Things I won't work with: the higher states of bromine (2019)

https://blogs.sciencemag.org/pipeline/archives/2019/11/21/the-higher-states-of-bromine

by fanf2 • 2 years ago

385 103 2 years ago

blogs.sciencemag.org

Enjoyed it a lot, sounded like alchemy on the way to create gold.

labster• 2 years ago

Kind of like alchemy. Except alchemy would kill you very slowly with heavy metal poisoning, and this stuff would kill you very very fast in multiple ways.

nottorp2• 2 years ago

If you want non lethal, I remember Lowe had an article about something that wasn't explosive or poisonous... but it got complaints from the people in neighboring buildings because of the smell.

Edit: not sure this is the one I'm thinking of, because they were complaining about it in the neigboring village, but here's one:

https://www.science.org/content/blog-post/things-i-won-t-wor...

phantomathkg• 2 years ago

As someone who have only A Level (i.e. high school) knowledge of Chemistry, every time I read "Things I won't work with" it always brings a smile to my face, as if those dangerous chemical are being synthesis in dodgy situation like those in cartoon.

paranoidrobot• 2 years ago

(2019)

This is from Derek Lowe's wonderful "Things I won't work with" series from his long running blog.

Even if you're not a chemistry person, it's written in an accessible way, and usually quite humorous way.

I recommend his 2010 post on "FOOF" Dioxygen Difluoride from the same series.

[1] https://www.science.org/content/blog-post/things-i-won-t-wor...

jajko• 2 years ago

I know nothing from chemistry apart from high school stuff decades ago (and wasnt very good at it), but oh boy Derek knows how to write interesting stuff for laymen, read whole series since it gets quite regular mentions here.

This is how you make people interested in more difficult topics

dylan604• 2 years ago

My high school chemistry teacher used this approach, and I thank her for it. While maybe not at the same level of chemist, she did her best to make the subject much more approachable. My physics teacher had his humorous approach as well. I can still see his hand drawn sketches on the overhead in my mind.

robocat2• 2 years ago

If you want to read an amazing book from someone who sails the other tack and lovingly creates rocket propellants: https://library.sciencemadness.org/library/books/ignition.pd...

proaralyst• 2 years ago

This is such a good book, and it was very accessible as someone with little chemistry education.

marcosdumay• 2 years ago

Yeah. The earlier, more famous posts of the blog on the article were about stuff that this book gives up on using because it just can't be contained and similar.

Then the blog goes into more and more dangerous stuff...

The silver lining is that the more dangerous a substance it, the lower the odds of it actually harming anybody, because everybody reacts like the author.

tlwr• 2 years ago

Always puts me in the mood to read the imitable "Excuse me sir, would you like to buy a kilo of isopropyl bromide"

chx• 2 years ago

Ah yes the timeless classic which at the end calls out an idiot company for offering something that explodes at -180C in commercial quantities :D

nraynaud• 2 years ago

I love how many of those blog posts are triggered by German articles. German chemistry: the best outcome is setting grant money ablaze.

RCitronsBroker• 2 years ago

https://www.uni-muenster.de/news/view.php?cmdid=13282

sometimes the students are also set ablaze, 20 at once is actually rather impressive

isoprophlex3• 2 years ago

Anhydrous redistilled hydrogen fluoride? No thanks!

Mind you: this is the stuff that, on skin contact, doesn't just burn you. It will immediately move through your skin to fuck up your nervous system, your organs, and your electrolyte balance to give you a heart attack.

If this synthesis were to kill me somehow, I'd rather blow myself up than get sprayed with HF.

Refer to [1] for more, unless you're easily disgusted...

[1] https://en.m.wikipedia.org/wiki/Hydrofluoric_acid_burn

thaumasiotes• 2 years ago

It's the first thing in the series: https://www.science.org/content/blog-post/things-i-won-t-tou...

HF has actually been used right out of the cylinder for a long time in Merrifield peptide synthesizers. It's the traditional way to cleave the peptide off the resin at the final step, so there are actually a lot of people who've used the stuff. But it's in a dedicated apparatus that is (that had better be) well sealed, and people treat it with due respect. At a former employer of mine, there was an accident with one of these machines right before I joined the company. The shout "HF LEAK!" went out into the halls, and I'm told that the whole area set a never-to-be-equaled evacuation record.

qiqitori• 2 years ago

Last night I somehow dreamed I had a hydrofluoric acid burn. Reading this thread I remembered there was this rust stain remover product on US Amazon that is 3% HF. https://www.amazon.com/product-reviews/B000LNQNM0/

It's got great reviews (and I'm inclined to believe that this product will do the job). There's one 1-star review that stands out though: "Simply put. It doesn’t work and it was shipped leaking." Yikes!

isoprophlex3• 2 years ago

Who knows what was left of that 3% HF after it was shipped leaking... Maybe it was just mildly spicy water when delivered, and the poor amazon warehouse workers got to have most of the fun.

NoMoreNicksLeft2• 2 years ago

I thought surely you must be joking when I clicked on the link. Then I thought, ok, I'm a high school flunky, and I must be confusing this with the "don't go within a million miles of" substance that Walter White used to dissolve corpses and the one that I've read about repeatedly over the years that is immediately poisonous to human life even if you spill it only on a fingertip. But nope the 1-star reviews make it clear that I'm not confused. Then I start wondering how this can even be shipped with regular parcel services...

I finished up by thinking "he linked to the reviews, because the product is no longer for sale". So I click through the link, nope. $11/bottle. And not soem Engrishy label, looks like I could find it on the shelf at Home Depot or Walmart. Seriously, wtf.

tehjoker• 2 years ago

The feeling of danger browsing that page trying to avoid accidentally clicking the "Buy" button.

notherhack• 2 years ago

"Improved" fire suppression systems contain hydrofluorocarbon gases which when burned decompose into HF gas. What could possibly go wrong?

Do NOT stay in the server room (or armored personnel carrier) when the fire suppression system goes off. https://academic.oup.com/milmed/article/177/1/108/4345530

thfuran• 2 years ago

That doesn't sound like an improvement.

fdr• 2 years ago

My dad had some interesting-acid stories, when he was a young chemist. They both involve cleaning glassware. The era is around 1970.

One was something he said resembled a wok full of the usual suspects of strong acids. Overnight, the mixture was hygroscopic, so they'd start it heating up in the morning to dehydrate it and increase the concentration. To test if it was ready, they'd throw in a small piece of wood, about the size of a match. If it disintegrated on contact, it was ready. Then you could dip your glassware to clean it.

But, in another lab, they would use a small bottle of hydrofluoric acid at the bench, taking a layer off the glass at the same time. While the dangers of large exposures were well known, he did mention the nerve damage and it being highly annoying and painful if trace amounts got under your fingernails, a somewhat common injury of the lab that everyone simply tolerated.

He thought the latter was a more convenient arrangement.

tonetegeatinst• 2 years ago

I'm a student in college studying cybersecurity but I have an interest in computer engineering.

I also have an interest in energetics. Florine is one of those chemicals you just got to respect. I know HF is used in the photoresist etch, and I'm interested in doing my own chip design. I realized that if I ever spilled HF on my, and the calcium cream didn't work, I'm better of just dying to anything other than HF. Iv heard its horrific to get on you in concentrated doses.

The price we pay for the small feature sizes on the wafer, and the increased density, in paid for in the usage of harsh chemicals.

raverbashing• 2 years ago

A thought about this:

Maybe in some far away galaxy, in a planet with much lower temperatures, intelligent life has evolved based on reactions like these, and some chemist there is writing about how long chains of carbon and hydrogen are for the most part useless as they're solid and inert at their temperature

maxbond• 2 years ago

Tangentially, once I watched an entertaining listicle video about the most dangerous chemicals on a popular science YouTube channel.

Years later, I stumbled on "In the Pipeline" (via HN), and realized the listicle was plagiarized from "Things I won't work with."

I don't know if there's a lesson there, but that's what happened.

mrandish• 2 years ago

This series by Derek Lowe is absolutely some of the funniest hard science writing I've ever had the pleasure of reading. That may sound like a low bar but make no mistake, this is truly great stuff. I've read the entire series of 33 articles going back over two decades and I only wish there was more (Derek is regular columnist but only occasionally posts new entries in this series).

Here's a good starting point: https://www.science.org/content/blog-post/what-here-compound... and a direct link to an index of just his "Things I Won't Work With" posts: https://www.science.org/topic/blog-category/things-i-wont-wo...

tanepiper2• 2 years ago

I once remember sitting in a Physics class, they shared with Chemistry and as we're sitting there one of the chemistry teachers started clearing up - not sure what happened exactly but all of a sudden there's a bang, red smoke and everyone starts coughing - we had to evacuate the entire section.

Turns out the teacher had poured some bromine down a sink, along with something it reacted with.

HarryHirsch3• 2 years ago

That is a strong indictment of US teacher training. (One assumes that's the US, because teachers are remarkbly untrained over there.) Everyone knows you deactivate bromine and chlorine with thiosulfate or sulfite and only then chuck it down the drain.

fuzzfactor• 2 years ago

This could also be the common error where someoone tries to pipet bromine like it was an ordinary liquid:

Open the bottle (under the hood), there's not that much red smoke coming out, dip the pipet into the dark liquid, pull in a few mLs, looks normal, almost like you could precisely dispense small amounts into the nearby target apparatus.

Lift the pipet slowly out of the source bottle, and carefully position it over the waiting reciever flask. Don't be too concerned about exact amounts to be dispensed any more, it can be seen that precision with bromine is not as ideal compared to something like pipetting alcohol, where you commonly lose a few drops anyway.

After all, immediately when you withdrew the pipet from the bromine bottle, the entire contents of the pipet had spewed out from its own gas pressure, into the inside of the hood. Don't worry about the state of your reaction, not a drop of bromine landed where you had intended.

All you can do if you have your wits about you is to hold your breath, carefully put the stopper back on the bromine bottle (without knocking the whole thing over) and fully evacuate, basically following out behind everyone else in other parts of the lab who knew there was a problem as soon as you did, just from the smell.

And that's with the best of hoods.

edit: not my downvote

tanepiper2• 2 years ago

No, this was in Scotland

dekhn2• 2 years ago

My strongest memory of high school chemistry is inhaling bromine vapors (I'm sure we were doing various addition reaction common in organic chemistry). It's got a very specific smell, rarely if ever encountered in the regular world.

The same chemistry lab had a sign warning us not to "pipette by mouth", but I actually do that today to transfer tardigrades. It gives you remarkable control over the volume transferred.

FreeFull2• 2 years ago

I guess accidentally getting tardigrades inside your mouth isn't anywhere near as bad as getting concentrated sulphuric acid in your mouth.

mnemotronic• 2 years ago

Apparently organic chemists speak a different kind of English.

moi2388• 2 years ago

What an absolute joy to read. I don’t know all the terms used but my god does this make me want to learn more about chemistry

G3rn0ti• 2 years ago

well, to the stuff described in this new paper., from Konrad Seppelt at the Freie Universität Berlin.

Prof. Konrad Seppelt became kind of famous in his community for creating various exotic Xenon substances including the world’s first compound between a noble gas and „noble“ metal.

He has been working with elemental fluorine for decades — so I guess he knows how to deal with dangerous stuff.

pfdietz2• 2 years ago

Xenon difluoride is in fact not hard to make: mix xenon and fluorine and expose to sunlight (or an artificial UV source). It just wasn't done for the longest time because of preconceptions.

teppic• 2 years ago

…you will at all times want to be suited up like you're going to going to spay a velociraptor.

Ha!

ethbr1• 2 years ago

Typo aside, that's one of the more clarifying similies I've ever read.

Or at least, for anyone who grew up on Jurassic Park: https://m.youtube.com/watch?v=WgQe68kF_8M&t=31s

Joel_Mckay4• 2 years ago

There are a few things that have a pucker-factor beyond most sane peoples limit. A few people do die every year from accidents handling hazardous chemicals. Some have a bit of time to regret their mistakes, as they say goodbye to friends and colleagues.

Every clown that gets cavalier with safety rules should read the story of Karen Wetterhahn. I can't think of a worse accident except maybe Louis Slotin, as it reads like it is strait out of horror fiction.

Some scientists literally die for their work. Have a wonderful day =)

inimino• 2 years ago

Wetterhahn

Who, just to be clear, was not being cavalier, but followed all the relevant precautions known at the time. They were just inadequate.

Joel_Mckay4• 2 years ago

There was some controversy over the details, but it was a terrible way to go.

Most people are trained from day 1 that PPE is never perfect.

krisoft2• 2 years ago

Every clown that gets cavalier with safety rules should read the story of Karen Wetterhahn.

I don't understand what you are saying. Karen Wetterhahn meticulously observed all known precautions at the time. Her death was terrible, but as far as we know zero "clowning" was involved. Shouldn't someone who "gets cavalier with safety rules" study cases where someone gets hurt after they "gets cavalier with safety rules"? There is plenty of those.

The lesson of the Karen Wetterhahn incident is that "Do everything right and by the book? The gru can steal eat your face." Not really the thing clowns should focus on.

Joel_Mckay4• 2 years ago

Everyone has a risk profile, and some people's hubris blinds gauging those limits.

ceejayoz• 2 years ago

"Someone who followed every known rule perfectly still died horribly" should especially give the people who get cavalier about the known rules some pause.

dekhn2• 2 years ago

The very first day I showed up for grad school, the entire hospital was closed off by men in hazmat suits and a bunch of firefighters. I proceeded to the central office of my program, where more men with hazmat suits were wandering around, and a guy was being treated in my program's office for injuries.

It turned out they were doing "spring cleaning" and somebody accidentally jiggled an old bottle of ether in a fume hood, and unfortunately the old ether must have had some free radicals, which led to an explosion. It blew out all the windows in the room (which were 20-30 feet away) and the chemist was only saved because he was wearing safety equipment (he still had permanent scars on his face years later).

That room was later my office! The incident (as well as the investigation) is written up here: https://synapse.ucsf.edu/articles/2019/03/24/date-ucsf-histo...

sierra10117• 2 years ago

I used to work in a genetics lab, and had to prepare trays of gel to visualise DNA tests (PCR testing to identify HLA alleles: effectively like finding someone's blood type, but for their immune system).

The compound in the gel that attaches itself to the DNA particles and makes it so we can visualise the results by UV fluorescence is Ethidium Bromide [1], one of the lower state Bromine salts the article mentions.

The way the electrophoresis gels are (were, by me and the other workers) prepared is by... microwaving a flask with it in. Repeatedly taking it out as it gets hotter to mix it. Usually involving some release of steam. Which includes a small amount of the bromide. Fine in small doses, but when you do it multiple times a day, 5 days a week, 45 weeks of the year...

To this day I wonder how much of an effect it's going to have on me and my colleagues at the time.

[1] https://en.m.wikipedia.org/wiki/Ethidium_bromide

Zeratoss• 2 years ago

The author actually has an article on that specific compound. https://www.science.org/content/blog-post/myth-ethidium-brom...

Not saying chronic exposure can never have adverse effects

fifnir• 2 years ago

My PhD supervisor would wash his teeth over the sink where we'd rinse all the gel preparation tools. He got throat cancer in his 50s and died soon after my PhD defense.

voidmain0001• 2 years ago

So, are you suggesting that the gel was the cause of the cancer for the supervisor? If so, was that sink’s drain connected to a diverter such that the waste didn’t enter the typical sewage system?

COGlory3• 2 years ago

Ethidium bromide is actually surprisingly not mutagenic

https://www.science.org/content/blog-post/myth-ethidium-brom...

isoprophlex3• 2 years ago

I don't want to hear any of these stories, considering I am a very clumsy person AND considering that I synthesized polycyclic aromatics. Thank god I got out after a couple of years, but sometimes I wonder what is still floating around in my DNA...

perihelions• 2 years ago

- "attaches itself to the DNA particles"

This is why it's a known mutagen with a long list of very specific, strident toxicity warnings. That's the organic cation, though; compared to that, the Br- anion is utterly benign. You're looking at the wrong hazard!

Br- is a standard counterion in human-approved drugs (those formulated as HBr salts).

https://www.google.com/search?q=hydrobromide+site:drugbank.c...

pfdietz2• 2 years ago

Bromide ion is in fact essential to animal (including human) life. It's necessary in trace amounts for the production of a weird S=N double bond in collagen IV, in a process where it is briefly converted to the BrO- ion (the +1 oxidation state). This was only discovered fairly recently; getting a fruit fly diet sufficiently depleted in bromide for the deficiency to show up was difficult.

Sea salt should have a fair amount of bromide in it. Bromine can be produced commercially by bubbling chlorine gas through sea water.

sierra10117• 2 years ago

Apologies, I was writing this while balancing my son on one arm and mixed up some simplification with good old-fashioned mistakes!

I'll nip this in the bud and say "DNA particles" was definitely the wrong word.

You are correct, the Bromine here isn't really the problem; the fact that any intercalculation with DNA occurs is the main problem. Is it Bromine's fault? Not particularly, but it's an accessory in this instance. Based on anecdotal evidence it's common to the electrophoresis process.

My reason for bringing this up is just one of those relatable stories (/s) about why I also don't like working with Bromine (even if contextually it's not Bromine's fault, we love you Bromine!)

flobosg5• 2 years ago

I also had to prepare agarose gels with EtBr in the past, but now there are several alternatives for gel staining, such as SYBR Green.

kjkjadksj2• 2 years ago

Which is able to stain because it intercalates into DNA. The same reason why etbr is seen as mutagenic by some.

sierra10117• 2 years ago

Luckily I've been out of that particular game for a few years, but it's good to know that less questionable options are available

COGlory3• 2 years ago

Add the EtBr after you microwave the agarose

flobosg5• 2 years ago

And cover the flask with some shrink wrap (maybe with a tiny hole punched into it) to hinder steam release.

sierra10117• 2 years ago

Yeah, that is always an option. However once boiling hot, if you introduce something into the flask it's more likely to create an explosion front. A bit like when someone supercools a bottle of water and then taps it to make it freeze; except with exploding sticky gel, and it's as hot as lava*

*Not actually as hot as lava, but wow does it feel like it

ChrisMarshallNY• 2 years ago

He's a great writer.

you will at all times want to be suited up like you're going to going to spay a velociraptor

Wins teh Internets.

coisasdavida• 2 years ago

I had read his post about Dengue a few days back, but hadn't looked at other posts, this guy is hilarious! The two articles about not enough nitro groups are great!

jokoon• 2 years ago

Isn't bromine used for anti cockroach gel?

EDIT: no, it's boric acid, B, not Br.

drunkonvinyl• 2 years ago

I love all of these. I have practically memorized this one: https://www.science.org/content/blog-post/sand-won-t-save-yo...

HarryHirsch3• 2 years ago

PSA: try the Chemical Force Youtube channel. It is run by a crazy fellow who demonstrates all sorts of esoteric and highly exothermic inorganic chemistry.

mastersummoner• 2 years ago

"it inevitably explodes"

Sums this whole thing up quite nicely, I'd say.

water-data-dude• 2 years ago

Here’s where the broken link from the first paragraph should go (I’m pretty sure):

https://www.science.org/content/blog-post/not-do-bromine

DylanSp• 2 years ago

Yep, that's it. A lot of links to other blog posts on older posts are broken, but you can usually change the "blogsdev" subdomain to "blogs" and it'll work.

jprete2• 2 years ago

That story is bonkers. I don't know how any student of chemistry mistakes a rocky crumbly cream-colored solid for an extremely hazardous red-orange liquid with a literal aura of evil wafting off of it.

RadicalEllis• 2 years ago

Wait until he hears about the even higher states of Iodine

gus_massa• 2 years ago

I have a specialization in Chemistry in my high school and we worked with Iodine and Bromide. IIRC Iodine is weak enough to be use as a desinfectant.

We used Bromide only oncde, probably disolved in carbon tetrachloride. A drop fell on my skin and it started to inch/hurt inmediately. I washed it imediately. It was not bad, just a whiter spot in the skin and some inching for a few days.

I'm more afraid of Bromide than Iodine.

jprete2• 2 years ago

I always enjoy Derek Lowe's "Things I won't work with", but I have to admit they're getting a little stale for me (although of course this was from 2019 and it wasn't stale then).

A writer can use the structure of their writing and word choices to hit certain emotional beats, and Lowe is quite good at this. If the actual content isn't quite substantial enough, though, the structural elements ring hollow to me because I've seen a lot of them.

It's directly analogous to clickbait titles, and also the subtle increase in head size, eye size, and emotional affect in YouTube thumbnails. The structure is used to encourage a level of emotional reaction in the consumer that the content of the title and/or thumbnail can't support in a more realistic style. But it starts to grate after a while.

yread• 2 years ago

Is there "Things I don't work with" series for programming? Alpha-quality compilers, non-ACID databases, legacy code full of race conditions, CSS (jk),...

chopin• 2 years ago

Aspect oriented programming.

60secs• 2 years ago

"bromine fluorine dioxide"

That's 3 reactive back-to-back no-thank-you's.

AstroJetson• 2 years ago

One of his articles has this line that is a personal favorite:

I know that sounds like the guy at the pet store packing a starved Komodo dragon into the carrier with your new dog, just to calm him down some.

Things I won't work with: the higher states of bromine (2019)

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