The Higher States of Bromine
blogs.sciencemag.org
blogs.sciencemag.org
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 . . .
It leaked, and the entire science block was evacuated.
By sticking the reaction mixture, bromine and all, on a rotavap. Outside a fumehood.
Or if you say "well, you can't", do you know how the manufacturer gets it in the bottle?
https://www.flickr.com/photos/53243414@N00/3941298659/
https://www.wew.de/en/news/archive-20152/new-bromine-iso-tan...
Then often pressure transferred under inert gas into progressively smaller lead-lined or Monel cylinders.
These are closed systems as much as possible.
Then somebody who really wants it in glass finally pressure transfers into an open container, decent amounts can be dispensed under its own pressure.
In a regular glass-stoppered acid bottle it can best remain under a hood, or underhood cabinet after that.
To get a few milliliters from the bottle you carefully pour the smoking liquid into a small graduated cylinder.
While suited up for dinosaur vivisection sans anesthetic in a toxic fog.
It's basically impossible to make the most precise measurements of such volatile materials anyway.
Then if you're making bromine water, once it's diluted it's not expected to come out exactly the same concentration every batch, you're either going to standardize it or run blanks each time.
Or you pipette it hastily, leaking some drops along the way. Which of course is a bad idea as it's not very safe, creates a bit of a mess and means your final volume is lower than intended. That is often what happens when students aren't warned about this behaviour of Bromine. It's not terrible (not good of course either) from a safety point of view, cleaning up some drops of Bromine in a fume hood is straightforward. Unless you don't work in a fume hood, which you and other people in the room will regret very quickly.
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
>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
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.
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).
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.
If you’re just dealing with interop with char*, std::string, Qt, LibICU, etc. it’s a nightmare.
Writing a URI parser in C which extracts hostname, port, and path is about the upper limit of what I want to do there.
I've done it, it works, I learned about strstr(3) in the process, and I don't want to do it again.
http://man7.org/linux/man-pages/man3/strstr.3.html
> Anybody who claims they've got amazing new data- or media= compression technology and wants funding for it.
Encryption is probably worse for snakeoil, but I like reading about crypto snake oil. Schneier has a good series on it called The Doghouse. Example entry:
https://www.schneier.com/blog/archives/2019/09/the_doghouse_...
Phil Zimmermann (PGP) has an essay on recognizing it:
https://philzimmermann.com/EN/essays/SnakeOil.html
djb even has a competition:
Anyone whose business plan names an existing famous company — “Uber for aircraft”, “Facebook for political activists”, that sort of thing.
More generally if your business model is "X for Y", where X is an existing company, you've possibly a lazy and uninspired USP which can easily be copied and your only real selling point is having the first-movers advantage and hopefully enough capitalisation that you can lead the market before the competition. You're just copying a business model and applying it to a different market, it's often a solution in search for a problem.
I could make an Uber for farriers (the people who put horseshoes on horses), but is there actually a need? Do horse owners currently have a problem finding farriers? And if they did, some other company could easily make a competing app, and if they had more capital and resources could easily crush Horse-Shuber.
In almost every spiel I've heard as an "Uber for X" it has been a delivery service.
The usage of a pre-existing company name is meant to mislead people into using their service. This has been a common practice for a long time, which is one of the myriad reasons why we have things like trademark laws to curb such language in advertising (in which a sales pitch counts as such.)
I've been guilty of the same thing roughly 15 years ago. Once I realized the wrong I was actually committing, I stopped. I've got a strong sense of justice/fairness, and the usage of another company's name to hawk your similar yet wholly unrelated service rang wrong with me once I understood the history behind the laws.
People have been saying “the $brand of XYZ” forever and quite frankly there is nothing wrong with that at all.
They are corporations, corporations don't have morals apart from "maximise profit".
On the specific question of medallions, medallions have the ostensible purpose of managing traffic congestion. Libertarians contend that this reasoning is just a cover for rent seeking by suppressing competition. Libertarians have been proven wrong by the huge increase in traffic in NYC as ride hailing congests the streets.
Brand new sentence...
PS: If you must do battle with the likes of strcpy(), avoid strncpy() and strlcpy() and head straight for strscpy()
It's NurdRage that lost his lab and is doing stuff in his bathroom again.
Best chemistry-related description since the one in Ignition about running shoes as vital lab equipment.
[1] the screw up was I had left the HF open (but not pulling) for 20 minutes instead of 5.
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.
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.
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.
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
And I was clear that setup matters in my gp.
How is that safer than neutral-pressure, aqueous HF? I'm perfectly comfortable with bottled HF, to the point that I literally handled it in the dark (light-sensitive samples), but I'd never set foot in the same room as a pressurized HF gas canister. A spilled HF bottle is a major incident, but ultimately straight forward to contain, whereas an HF canister leak would kill off an entire lab.
I've done enough manifold setups and worked with enough gas cylinders to understand that they can leak in all kinds of ways, even with a wealth of experience. As I said initially: you are definitely not paranoid enough about this setup.
>It’s sold compressed in metal cylinders, like other gases, but it needs some care in packaging. The stuff is so corrosive that special alloys need to be used, usually ones high in nickel. If you stick an ordinary gas regulator on top of an HF cylinder, you’re in for trouble, and the complete destruction of the regulator is the least of your worries.
>HF has actually been used right out of the cylinder for a long time in Merrifield peptide synthesizers.
[1]: https://blogs.sciencemag.org/pipeline/archives/2004/03/03/th...
But hey I worked with 100% HF for seven years (BOC protected amino acid synthesis), so what do I know...
If you have a 5% aqueous solution most of that HF is still binary undissociated HF, which will leak into the atmosphere so you could very easily unawaredly be breathing it in if you are working with it in any open air situation below the sash line (which is what the tendency is when you're working with aqueous concoctions).
Even working at negative pressures, you can easily end up with a positive-pressure manifold if your sample is unexpectedly evolving gas at a higher than usual rate, or your valves aren't configured as intended. To be clear, these aren't academic exercises; I've actually seen all of these happen. With closed systems, you have to anticipate explosive pressures and plan accordingly. HF is incompatible with that kind of failure.
Guy spills a beaker (100-250 mL) of HF on his thighs. They end up amputating his leg but he still dies anyways.
Yes, mistakes will happen. Yes, you can segfault erlang. Yes there are tradeoffs. But, I can have a junior deploy to prod confidently in a BEAM language in a few months, I can have a first year grad student use HF confidently in a few weeks.
On the other hand (pun intended) chemicals intrinsically make a burn more or less serious. It's the difference between getting a rash or dying a horrible death.
In a risk matrix the probability has less weight than the severity. So a "catastrophic" severity will make the risk shoot up faster than even "certain" probability. Regardless of tooling and precautions taken the impact of the mistake makes a difference in any field and will make people want to completely steer away from some.
I think it can be summed it up like this: If you were tied to a chair and someone was about to drip something on you what would you rather it be: HCl or ClF3?
But you're being pedantic now. Nobody takes the plane to a place they can walk to. Many people don't take the plane even to a place where they can go by train or car. I understand that you may have to work with something like ClF3 but what everyone is telling you is that they'd rather avoid it if they have a choice. Just like most people would avoid working with unstable explosives, dangerous pathogens, extreme sports, and any very dangerous job in general even if all of these have their own set of precautions.
As the danger level increases people justifiably would rather avoid that specific task. Precautions are a mitigation but overall the sentiment stays, the job becomes much more stressful and the outcome of a mistake more severe.
The more dangerous the task and more severe the consequences of a mistake, the fewer the people that would want to deal with it. Take from this what you will.
> Before the 1970s, silanes were considered unsuitable for use as fuels, because they instantaneously self-combust at room temperature. Not satisfied to leave it at that however, Plichta went to work and succeeded in producing longer-chained silanes that appeared as clear, oily liquids and were stable at room temperature.
~ https://www.offgridquest.com/energy/turning-sand-into-fuel-s...
It burns nitrogen and the reaction is so energetic the flames are lighting.
Bromo alkanes are known alkylating agents. Some alkylating agents are carcinogenic. YMMV...
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.
https://blogs.sciencemag.org/pipeline/archives/2014/09/22/a_... - A Free Online Med-Chem Course
The course appears to now be at https://www.coursera.org/learn/drug-discovery
Removing Thiomersal from vaccines didn't reduce ASD diagnoses. That seemed to be sufficient for me to form a judgement on it. But, AIUI it's not used in vaccines in the UK now anyway.
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/2008/02/26/sa...
> The biggest stinker I have run across. . .Imagine 6 skunks wrapped in rubber innertubes and the whole thing is set ablaze. That might approach the metaphysical stench of this material.
https://hn.algolia.com/?&query=pipeline.corante.com%2Farchiv...
https://hn.algolia.com/?query=http%3A%2F%2Fblogs.sciencemag....
That was worth the read. Thanks!
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.
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.
Using zinc would have been much less dangerous.
They say bromine stands in for iodine, which is critical for many things.
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).
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!
However, pouring unspeakable amounts of money, watts and person-hours into completely unnecessary and wasteful infrastructure just because emergent properties of a system mean that billion dollar companies and their owners can make a lot of money by being a picosecond faster than each other in an eternal battle is of extremely questionable utility.
What exactly do we as a society get in exchange?
Arguing about HFT feels like you're questioning people about why they're spending billions on excavating single, individual sand grains and the defense you get is "well, sand is an incredibly important building material. It is used in concrete, and we wouldn't have modern society without it". Sure that's true, but why is it that nobody can tell me how what you're doing is actually necessary for that.
Does that require HFT, or just T?
That's the theory, anyways.
No.
Market event A is seen to correlate strongly with market event B. The correlation is so obvious that multiple participants compete to make the B trade first in reaction to A. It's part of having a healthy market, electronic or otherwise.
Besides the definition of what constitutes a "white supremacist" has been getting more ambiguous by the minute over the past few years. Nowadays it pretty much just means "anyone who doesn't like illegal immigration" or "anyone I don't like, but I'm too lazy to articulate why".
Your post is similar to if I proposed a hypothetical about addition using apples, and you posted a screed about how apples are overused in American cuisine and their nutritional value is suspect, especially relative to oranges and pears.
Just the other week I saw the news that until recently we had 300 (!) Saudi nationals training to fly planes right here in the US. Software won't help us with stupidity/sabotage of this magnitude.
https://abcnews.go.com/Politics/navy-suspends-flight-trainin...
I'm not in favor of surveillance panopticons either, for what it's worth.
Still, that's very few events, which supports my point. It's basically a more potent "think of the children" trojan horse that routinely gives the government even more power (and potential for abuse) through harebrained and ineffectual laws. See e.g. the current FISA abuse scandal where the FBI _falsified the supporting documentation, and knowingly supplied fake documentation to the court_ to spy on a presidential campaign. Had it been you or me they spied on, nobody would even know.
Again, I agree with you that domestic extremism (be it white supremacist, Muslim, or Black Hebrew Israelites) should be countered through ordinary policing, rather than building the Stasi's wet dream.
There is just no way that doesn't already happen all over the place already.
The "things I won't work with" blog lists things that will actually kill you in horrible, mind bendingly painful ways.
In Tech it's more like "things I won't work with because it might fail" or "is too difficult" or "might be a bit too unscrupulous"
For some of things, sure.
But there are other things that do cause death, pain and suffering.
If you wrote code that's used in military weapons, that's a more direct relationship.
If you write code that's used to power gambling sites/devices, it's perhaps somewhat abstract - but there are a large number of people who are harmed because of how addictive these things are.
If you write code that's used for managing high-interest loans (like the point-of-sales type of 'buy-now-pay-later' of loans) - then you're enabling the exploitation of people who by-and-large cannot afford the things they're being told they can have, and will spend a large portion of their life paying these loans off.
Being true to one's own ethics is a very worthy virtue. But it just isn't in the same league as not wanting to melt one's face off or accidentally die in a paralysing seizure of excruciating pain.
For most of the things, my personal opinion on wanting to work for the ones you've listed are definitely in the "it depends on the organisation/management" category.
If it's a company that is (in my opinion) causing more harm than good, then it's not somewhere I'd want to work.
The point of my post was to point out that some tech roles are for companies who do cause harm/pain/suffering whether that's direct (military) or indirect (loan sharking).
Whether the military or an arms manufacturer is necessary is a whole other debate - but the whole point of those types of organisations is the ability to directly cause harm to those they're directed at.
However organisations that provide high interest credit to those who can't afford the thing they're buying, with the intent to keep milking money from their debtors do cause suffering, albeit in a more indirect sense.
I am ok with defence apart form Chem and Bio, "that just sqicks me out"
Though it does depend on who id be working for I did turn down a recruiter who was looking for people to work on the MET police Registry, but I would have worked for HMGCC.
Note these where both Avowed Jobs so I am not breaking any laws mentioning them.
That's sort of the point of ethics though, it's pretty weak to say "I choose not to steal because it is wrong, but you do you."
Perhaps they're two degrees of the same thing, but it doesn't seem obvious to me.
I think there is also a subset of the first: things which I don't think anyone should be doing but social pressure forbids objection - eating meat comes to mind. Abortion may fall into this category for some, but in my experience even in fairly liberal circles people are willing to object to abortion, they just tend to couch it more.
Should the creators of Gmail or Word or etc feel bad because therapists are using their services to send their notes to colleagues?
Online voting. Anything more sophisticated than automated scanning of a paper ballot cannot be trusted, even in theory. Always, always be able to do an audit from the original ballots.
The bad thing about dangerous tech is that it is usually someone else who gets hurt, and the technologist is affected last or not at all. Predictive policing? It's not going to be rich white guys who catch the pointy end of that stick...
It should probably be required by law that Zuckerberg keep nude photos of himself on his Facebook account, to encourage security.
Detection of white collar crime? Surely detection of fraud in financial transactions isn't rocket surgery...
Interestingly, this has probably been the main beneficial effect of the GDPR so far. Personal data has shifted from being a pure asset to a combo of asset and liability, causing some companies to just avoid collecting anything but the essentials.
Computer tech is nowhere near as spectacular as chemistry, in an immediate, palpable sense. Almost nothing is. Maybe some narrow areas of physics or real-world engineering. But chemistry is pretty much unique that way.
Chemistry is a great hobby to pick up when you're a teen. Well, assuming you survive the whole thing.
So... No EHRs?
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...). 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... and https://hn.algolia.com/?dateRange=all&page=0&prefix=true&que...)
If anyone wants to read (a lot) more about title changes on HN, some recent things are https://news.ycombinator.com/item?id=21617954 and https://news.ycombinator.com/item?id=20429573.
Thank you to you, Scott, and everyone else for keeping this site so wonderfully curated.