
The Higher States of Bromine - Karunamon
https://blogs.sciencemag.org/pipeline/archives/2019/11/21/the-higher-states-of-bromine
======
fuzzfactor
Keep in mind the risk with just regular liquid elemental bromine.

Seems like a heavy red nasty fuming liquid because it is.

Concentrated nitric acid is heavy too, has aggressive red fumes of its own
kind but it is a clear liquid.

And you can pipet nitric acid.

But you can't pipet bromine.

If you try it, you might think so at first since bromine can be drawn up in to
the pipet like any other liquid, but once you remove the pipet from the source
bottle, it expells itself from the pipet before any transfer can be made. With
nature at work, it begins destroying anything it had come in contact with,
while the majority of the carefully measured quantity rapidly evaporates and
instantly triggers the evacuation instinct with great encouragement.

Even when handled under a fume hood, where most of it goes up the hood, people
at the other end of the lab will be out the door in less than one second after
the first whiff.

Don't ask me how I know but there was this graduate student who was a little
bit of a loose cannon . . .

~~~
dschuler
How do you move it around if you can't use a pipette?

Or if you say "well, you can't", do you know how the manufacturer gets it in
the bottle?

~~~
saagarjha
Some precise pouring, maybe?

~~~
fuzzfactor
Things like this you try not to spill a drop.

Sometimes more is spilled, take a look at this, where a noticeable release in
Shandong was being filmed from a _safe_ distance when it got worse fast and
filming continued whilst fleeing. Footage was then stabilized by a reddit
viewer:

[https://gfycat.com/aggravatingagileherring](https://gfycat.com/aggravatingagileherring)

>Xinhua News Agency, Jinan, May 9 (Reporter Zhang Zhilong) The reporter
learned from relevant departments of Shouguang City, Shandong Province that at
around 14:00 on May 9, the bromine tank of Shouguang Yumeng Chemical Co., Ltd.
was tilted, and part of the bromine leaked. Short-term red smoke band. No
casualties.

> After the accident, Shouguang City safety supervision, environmental
> protection and other departments immediately rushed to the scene to assess
> the disposal. At present, the site has been disposed of and the cause of the
> accident is under investigation.

> It is understood that chemical bromine is a red-brown fuming liquid that has
> strong irritating and corrosive effects on the skin and mucous membranes.

Google translation of source
[http://www.xinhuanet.com/2018-05/09/c_1122808340.htm](http://www.xinhuanet.com/2018-05/09/c_1122808340.htm)

Glad only a small part of it overflowed, wouldn't want a significant incident.

What you see here is just the spill, not a result of chemical reaction or
other runaway condition.

------
OliverJones
I started out a biochemist before I discovered computers. This article is rofl
funny. "invigorate itself all over the ceiling..." yeah, got the t-shirt.
That's why they took away my bunsen burner and gave me a mouse.

Seriously.... fellow programmers, designers, entrepreneurs. What are the
things you won't work with?

For my part:

Web code written in any language without a well-integrated string data type.
strcpy() is a target painted on my back if I did that.

Anybody who claims they've got amazing new data- or media= compression
technology and wants funding for it.

Transferring peoples' data from a protected realm (like a HIPAA-covered
pharmacy system) to an unprotected realm (like direct marketing).

~~~
ajuc
The only thing worse than no good string data type is 5 different string data
types in one application.

std::string, OString, QString, char*, QByteArray

OString was our wrapper around database library strings.

And there were automatic cast between SOME of these. I especially liked the
helpful automatic cast to bool from OString (true if it wasn't empty if you're
wondering). It meant that doing OString("password") == OString("wrong
password") returned true because it converted both to bool.

~~~
adrianN
Five different string datatypes are actually a good idea in many scenarios,
but you have to be very careful with automatic conversions.

~~~
klodolph
I think five different string datatypes are reasonable if they’re types like
String, HTMLFragment, JavaScriptFragment, etc.

If you’re just dealing with interop with char*, std::string, Qt, LibICU, etc.
it’s a nightmare.

------
twic
There's a link in the comments to some nutter who does mildly horrifying
syntheses on YouTube, like this one for chromyl chloride:

[https://www.youtube.com/watch?v=saANxD0cqy0](https://www.youtube.com/watch?v=saANxD0cqy0)

~~~
sq_
Wow. I just watched that one and his toilet paper moonshine video. I can’t
believe he’s doing all of this in a home lab!

~~~
emikulic
These days he rents a commercial space. He's done videos on setting it up.

It's NurdRage that lost his lab and is doing stuff in his bathroom again.

------
sandworm101
>> ...a willingness to do things like redistill anhydrous HF, and you will at
all times want to be suited up like you’re going to going to spay a
velociraptor.

Best chemistry-related description since the one in Ignition about running
shoes as vital lab equipment.

------
dnautics
I do think derek lowe is a bit too paranoid about HF. I've worked with HF
before, and with a proper setup (negative pressure, calcium carbonate filter,
teflon equiment) it is really quite reasonable to handle. I would entrust a
conscientious first year grad student to it (as I was entrusted). I only
screwed up once [1], and the consequence was we lost about 1/8 of our calcium
carbonate filter column. You can tell because the section that has most
recently been expended is warm on the outside of heavily shielded carbonate
vessel).

[1] the screw up was I had left the HF open (but not pulling) for 20 minutes
instead of 5.

~~~
omar_a1
I think you're not paranoid enough about HF. It doesn't wash off, and is small
enough to pass through skin to form insoluble mineral precipitate with calcium
in bone and blood, which can result in amputations from dead tissue. It's one
of the few acids capable of eating through silicates in glass or rock.

Even at lower concentrations, you still need specialized gloves, apron, and
ideally a face shield, in addition to standard PPE. Source: worked with HF for
3 years.

~~~
refurb
Agreed.

If I had to choose splashing my arm with a concentrated acid, I would choose
sulfuric or nitric acid over HF.

Unlike the other acids that just burn the surface of the skin, HF rapidly
penetrated the skin and can mess up your potassium levels. Plus tissue
destruction is much deeper.

~~~
dnautics
That's why you keep calcium carbonate salve around. Also you're more vigilant
around hf. I've spilled conc sulfuric and nitric acid on my lab coats. HF will
never get that close, as safe equipment is in a closed loop but not that
complex or byrdensome (it's not like explosives research for example)

There are some idiots that use open air HF for etching. _That_ is a very bad
idea.

I should clarify by open in the description I meant valve open. The system was
still closed.

~~~
refurb
Fair enough. You’re using it in a certain way that makes accidental exposure
less likely.

I was speaking more generally. It’s not uncommon for labs to handle
concentrated HF in a similar manner as other acids - I.e. pouring it into a
beaker in a fume hood

~~~
dnautics
Yes this is a mistake but to categorically say that HF is scary and dangerous
actually creates, in my opinion, a mindset that is detrimental to operator's
of safe HF equipment and also encourages use of more wasteful (e.g. FMOC)
techniques which also have tradeoffs (nonsynthesiazbility is more of a problem
with FMOC than BOC).

And I was clear that setup matters in my gp.

------
api
A long time ago I found this series and LOL'ed and then had to email him a
link I found to an experiment in using fluorine instead of oxygen in a rocket
as an oxidizer. It resulted in the highest specific impulse ever recorded for
a chemical fuel and would be awesome were it not for the exhaust being pure
hydrofluoric acid.

~~~
pfdietz
I believe the highest Isp with fluorine is Li/H2/F2 tripropellant, in which
the exhaust is mostly hydrogen and lithium fluoride.

~~~
api
Well I guess if you need a flame thrower in hell...

------
perl4ever
I've wondered if I should be nervous about brominated vegetable oil in food. I
mean, it's not new or unusual, but I feel like if it was just invented, we'd
all be rather skeptical, no?

~~~
sansnomme
You know, philanthropists really need to invest in higher level free education
for non-CS sciences. We have tons of free resources with tremendously
beautiful animations on data structures and state-of-the-art machine learning,
but the same can't be said for bio and chemistry. This is holding back the
biotech industry. People can't make educated judgements about stuff like
Mercury Thiomersal because that level of organic chemistry understanding isn't
covered well by existing resources like Khan Academy. Hacker News and Silicon
Valley loves disruption and "Move fast break things" Uber-style. How about
democratising medical education? The cheapest, fastest way to improve
healthcare in developing countries is to break the whole "apprenticeship"
gatekeeping system that plague medicine and pharmacy. There is no FDA in
Africa to bring down the hammer on you making videos on low-cost quality
control for orphan drug analogues when people are dying due to corruption,
incompetence, and poor medical practices. The level of biochemistry knowledge
on HN is amazingly poor, every thread on CRISPR and gene drives reads like the
infamous parable of the blind men and an elephant.

~~~
harimau777
I would love that!

I'm researching materials for a project I'm working on so I've been reading a
lot of chemistry articles on Wikipedia. I've noticed that there appears to be
a set of known building blocks that chemists use to build solutions. Something
like:

\- "Molecule bits" (rings, chains, functional groups, esters, etc.) that have
known properties

\- Common processes for modifying/changing those bits (alkylation,
calcination, ether cleavage, etc.)

\- A set of standard chemicals (alcohols, acids, solvents, emulsifiers, etc.)

For example I often read things like:

"In order to give a polymer higher temperature tolerance, chemists often add a
benzine ring by calcinating the molecule using acetone."[1]

While I'm sure that a professional chemist needs to be able to handle lots of
edge cases, it seems to me that a lay person could get a lot of milage out of
learning these standard building blocks. I'm going to have to look and see if
I can find a good resource that explains them.

[1] Note: All of this sentence is completely made up, I just intend it as an
example.

~~~
whatshisface
That "good resource that explains them" would probably be an organic chemistry
textbook.

------
samatman
This entire series is a treasure.

I'll share my favorite, just for the phrase "Satan's kimchi" alone:

[https://blogs.sciencemag.org/pipeline/archives/2010/02/23/th...](https://blogs.sciencemag.org/pipeline/archives/2010/02/23/things_i_wont_work_with_dioxygen_difluoride)

~~~
rpeden
"Sand won't save you this time" is another great read from the series:

[https://blogs.sciencemag.org/pipeline/archives/2008/02/26/sa...](https://blogs.sciencemag.org/pipeline/archives/2008/02/26/sand_wont_save_you_this_time)

------
lostmyoldone
My high school teacher in chemistry was a bit of an original. Dedicated and
ambitious, and maybe a little bit crazy.

In our 2nd and 3rd year we did quite 'serious' organic synthesis labs,
including bromination of benzene, which of course included elemental bromine.
The teacher did ration it out in out small stoppered round bottom flasks, but
then we all did the synthesis in teams of two/three.

He was still very serious on security, and I guess his main reason for
including that lab was to make sure that all his students had understood the
seriousness of chemical dangers.

If you had done anything even slightly out of line in any lab, but especially
that one, you would absolutely have been sent home, and probably been advised
that maybe experimental organic chemistry wasn't for you.

Right or wrong, but that's the story about how I got to work with elemental
bromine in high school at the age of 16 or 17.

~~~
fuzzfactor
It can be an interesting head start at a young age.

I went to experimental school having more progressive and well equipped labs
than supposedly others at the time. Everything was new and advanced, we were
the guinea pigs. Not toxically by any intention, just behaviorally for the
most part.

I got to the university early and had excellent professors, ended up interning
when I was 20 at a leading research fluorochemical and silicochemical plant
that had been a startup from one of them years earlier. By the time I got
there they had a fluorine trailer on site, at times the only live one in North
America back then, so "no insurance for you".

We stocked experimental silanes, silazanes, fluoromonomers, and things like
fluorides of xenon in the main chemical room if they were under a few kilos.
Osmium tetroxide too, but only a few grams.

But there was another building with the real nasty stuff on the shelves, where
every single one of them was something most chemists would never want to see
the bottle open. Especially if they were the poor soul that had to do it the
previous time. Too bad a lot of the compounds would eat through the bottle cap
within a faily predictable period of months or years according to the
material, so somebody was going in there fairly regularly to accomplish cap
replacement as needed anyway.

You could tell when something was coming out more agressively than normal when
you walked by the building. It was easy to smell since it was built with the
cinder blocks turned sideways for ventilation, just like the numerous
systhesis labs scattered safe distances from each other, all far from the
heavy concrete blast embankment which faced off into the woods. Only the labs
didn't have actual doors in their four doorways. It didn't go without saying
that 4 ways out still might not be enough for a single chemist, and you can't
have any obstacles in your way. Firefighting training included extinguishment
through the flow-through walls into the dummy lab from the outside, which was
just a lab that had gone out of control but not been completely destroyed.

The agressive chemical storage had secure doors but it was still gagging you
with its smell-through open walls. How much worse could it get to actually go
inside? Well there was the thiophosgene. You think plain phosgene is bad, this
is not your everyday phosgene. It was rough, once you got to know it, largely
seemed like one of the main stench culprits. The bottle stayed in the room,
measurement was done right there. You had to put on a disposable suit to
protect you from the outer suit which was assumed to be contaminated from
previous tasks. Full face respirator and shield, rubber boots and spats,
multiple glove layers to open the crate, dig into the vermiculite for the can,
open with sparkproof tools, dig into more vermiculite for the bottle of ugly
red liquid its damn self. Any access to thiophosgene called for full
replacement of the bottle cap, can, crate, and vermiculite, so it could
hopefully be left alone as long as possible undisturbed afterward. Once opened
and repacked, that room smelled about ten times worse than normal for a couple
weeks even though the thiophosgene was sealed up like that.

Anyway, I have lived by my teenage decision but accept it as immature, I don't
recommend such toxic or dangerous work to others and carry on partially
because I want to use any unfair advantage for myself & others to handle risky
things more responsibly or not at all.

------
m0zg
Reminds me of "Ignition!", which is, if nothing else, a very entertaining
read. Those dudes out of necessity had to work with every dangerous and
explosive chemical known (and discovered a few in the process). At one point
in order to boost the thrust of engine they _sprayed liquid mercury_ into the
nozzle. Unsuccessful tests often meant that the building housing the rocket
motor would be demolished by explosion, often simply because some chemical ran
the wrong way in the tubing due to pressure differential or some newly
discovered rocket fuel or oxidizer had a reaction with some minuscule
contamination in the fuel or oxidizer line. There were also some proposed
fuels (butyl mercaptan) that smelled so foul, they had to evacuate buildings,
but that did not stop them from experimenting with them in a wooden shack 200
yards away from the main building.

~~~
pfdietz
They didn't spray mercury into the nozzle; it was injected into the thrust
chamber itself with the fuel and oxidizer. The point was to maximize "density
impulse" (specific impulse x density of propellants).

Using zinc would have been much less dangerous.

~~~
ncmncm
Somebody criminally contaminated a desert somewhere west of LA that way.

~~~
ncmncm
*east of

------
phkahler
From the comments: At least in the States you can have potassium bromate added
to the flour in your bread.

They say bromine stands in for iodine, which is critical for many things.

------
tectonic
They're all amazing. Here are past issues:
[https://blogs.sciencemag.org/pipeline/?s=things+I+won%27t+wo...](https://blogs.sciencemag.org/pipeline/?s=things+I+won%27t+work+with)

~~~
shoghicp
Better link pointing to the category, includes more results
[https://blogs.sciencemag.org/pipeline/archives/category/thin...](https://blogs.sciencemag.org/pipeline/archives/category/things-
i-wont-work-with)

------
nullc
If you enjoy reading about crazy chemistry, I recommend the book "excuse me
sir, would you like to buy a kilo of isopropyl bromide?" a 70's era
autobiography by a chemist.

[https://archive.org/details/gergel_isopropyl_bromide](https://archive.org/details/gergel_isopropyl_bromide)

------
jdnier
Here's the full list of "Things I Won't Work With" articles:
[https://blogs.sciencemag.org/pipeline/archives/category/thin...](https://blogs.sciencemag.org/pipeline/archives/category/things-
i-wont-work-with)

------
userbinator
The related linked article at
[https://blogs.sciencemag.org/pipeline/archives/2005/12/17/ho...](https://blogs.sciencemag.org/pipeline/archives/2005/12/17/how_not_to_do_it_bromine)
is also well worth reading.

------
nitrogen
I noticed that all of these reactions are performed at very low temperatures.
Could there be enough chemistry for life at these very low temperatures?

------
dekhn
I still clearly remember using bromine in high school chemistry lab...
horrible fumes. "Do not pipette by mouth".

------
johnhess
"Things I wont work with" is a great concept that tech should borrow from
chemistry. Some things, while they carry possible returns on investment, are
simply not worth the risk.

I wonder what "Things I wont work with" would be for tech. I can imagine
particular technologies (e.g. predictive policing) or types of data (e.g. I
refuse to put digitized therapist's notes on the internet).

~~~
malux85
No helping oppressive governments spy on dissidents.

No high frequency trading.

No financial targeting the vulnerable (subjective, use your own ethics and
good judgement)

No dragnets

No devices to disrupt tor or P2P networks

No troll farming or mass media manipulation

No fake dating profiles

No metric stuffing

That’s it off the top of my head. I know that sometimes secondary effects can
happen (e.g. an oppressive government may use a database, and I might work on
that database) but that’s not me directly helping them.

Something like this, feel free to add others everyone!

~~~
narrator
No fully automated slaughterbots. There has to be a man in the loop that at
least clicks a mouse every time the robot kills an enemy combatant. No one
should ever say: "Oh yeah, we had a bug in the auto-kill algo and our killer
robot shot a whole bunch of innocent civilians. Whoops! That's nobody's fault.
Nobody's responsible. The algo did it all by itself!"

~~~
blotter_paper
In the context of a military that accepts collateral damage as par for the
course, I don't really see the distinction. Did anybody but Manning go to
prison over that Collateral Murder video? We have humans approve airstrikes
that we _know_ will kill unidentified civilians when they're close to an
identified target. We have humans approve airstrikes that _target_
unidentified individuals which we probabilistically identify as combatants
based on movement and cellphone metadata. What difference does it make if a
human pulls the trigger --err, presses the button?

------
ComputerGuru
@dang and co: The old title with “things I won’t work with:” is both the name
of a series HN is familiar with and presenting in TFA as the category the post
was made under; perhaps it should be returned?

~~~
dang
We tend to remove names of series, as well as names of sites and other
repetitive markers from titles, in the interest of keeping things
unpredictable. An unpredictable HN is a good HN.

The fact that this is a "Thing I Won't Work With" instalment shows up
immediately in both the article and the comments, so the information is only
one hop away. Also, the article being at #1 is a strong clue that the content
is interesting to more than just chemistry specialists. It's generally good
for HN if not everything reveals its secrets right away, and readers have to
work a little
([https://hn.algolia.com/?dateRange=all&page=0&prefix=false&qu...](https://hn.algolia.com/?dateRange=all&page=0&prefix=false&query=by%3Adang%20%22work%20a%20little%22&sort=byDate&type=comment)).
When you have to do a tiny bit of work before getting the dopamine hit of
pattern-matching, it seems to put the brain in a slightly less predictable
state.

Before we changed the title, the thread was mostly about the series, not the
specific article. That's poorer for discussion quality, which gets more
predictable and less varied as topics get more generic. (For lots of
explanation of that phenomenon, see
[https://hn.algolia.com/?dateRange=all&page=0&prefix=false&qu...](https://hn.algolia.com/?dateRange=all&page=0&prefix=false&query=by%3Adang%20generic%20discussion&sort=byDate&type=comment)
and
[https://hn.algolia.com/?dateRange=all&page=0&prefix=true&que...](https://hn.algolia.com/?dateRange=all&page=0&prefix=true&query=by%3Adang%20lists%20common&sort=byDate&type=comment))

If anyone wants to read (a lot) more about title changes on HN, some recent
things are
[https://news.ycombinator.com/item?id=21617954](https://news.ycombinator.com/item?id=21617954)
and
[https://news.ycombinator.com/item?id=20429573](https://news.ycombinator.com/item?id=20429573).

~~~
Karunamon
Thank you for the explanation. I was debating on whether or not I should have
included the category when submitting this.. I leaned on including it because
it was right there on top of the headline, and figured nobody would find it
interesting enough to click without the pointer that it's a part of an
established, interesting series of articles.

