Things I Won't Work With: Peroxide Peroxides | Hacker News Reader

Things I Won't Work With: Peroxide Peroxides

pipeline.corante.com

128 pointsjoe_bleau53 comments

I was one of those kids that read that the original Bell jetpack used Hydrogen Peroxide with a silver catalyst for "fuel". I tried it on the peroxide I bought from the drug store and it didn't work. So I figured "oh it just needs to be more concentrated." My friend and I built a pretty crude still and about 10 gallons of 5% hydrogen peroxide. I don't know what the concentration was when we finished, but I do remember trying to pour some into a steel pipe which was to be our "tank" for our test rocket. To say that I was startled by the pipe being yanked out of my hand by the steam exploding out of its end would be an understatement :-) We spent the rest of the afternoon "blowing up" ant hills in the desert by pouring like a quarter up of our distillate on to them.

How? How!?

How is it you always have cool and relevant stories!?

I know, right? He's like a modern Tom Sawyer.

EDIT: It occurs to me this might not be taken as a compliment. I meant it as one, though: Chuck's always got some cool story to add, and I suspect his biography would be a heckuva ride.

I chalk it up to curiosity on my part and survivor bias on the stories part. Folks who have known me for a long time know that I am a very curious person and I spend an inordinate amount of my spare time reading and "investigating" things (which my wife calls puttering). But there is also a bit of survivor bias here, it only seems like it is true because I don't have any stories to share on a lot of things here and elsewhere and don't. Oh and I'm "old", so I've got a lot of time between when I started doing crazy stunts and now, so even doing only one every couple of years I've got double the number of crazy stories than a "young" guy :-). That said, I'm sad that during my high school and college years the (late 70's early 80's) it was so much easier for me to explore things, whether it was the high school district's shared mainframe, or home made high concentration HOOH than it is today. No doubt if I were one of my own kids growing up in the 90's I would have been arrested and my parents assumed to be poor examples of responsible adults.

Agree on the parent part. If I let my kids do anything remotely close to what I did as a kid, CPS would never let me see them again. I left in the morning and came back at dark, with no check in. I did experiments with things I learned in the Anarchists cookbook. Its amazing what you can blow up with household objects. You kids today have it easy blowing up stuff - just go on Youtube. In the early 80s you had to know someone to get the really bad somewhat illegible copy. My kids love watching Mythbusters when they blow things up. I wasn't sure whether to be happy or worried when my 8 year old asked for Polycarbonate blast shields. He was thinking of things he wanted to blow up, and how to do it. That made me worry. He wanted to do it safely and had given some thought to shield and remote triggering. That made me happy, i did not have the same focus on safety as a kid and burned my eyebrows off several times. As of today we have not done anything, he has got his attention on other projects and I am not going to bring it up.

TL:DR - typical 12 year old kid from 1982 would be labeled child Al Quaeda terror cell, parents would go to jail for 25 years.

I spent some time at the remaining facility in the country making the really interesting rocket fuel. The most fascinating thing to me (aside from the multiple armed security checkpoints required to visit the food lab we were visiting) was the setup of the buildings. Nearly all of them were ~500yds apart, set in between massive ~50ft tall, ~100ft wide earthen berms. The really interesting buildings had escape slides coming from the second floor. Each building at the roadside had the familiar NFPA diamond for response crews. I've never seen so many "4"s on that diamond in my life.

I used to work at a pilot plant that did large scale synthesis of pharmaceuticals. The plant was a concrete structure with each reactor surrounded on three sides by two foot thick concrete walls.

The interesting thing was that there was no outside wall to the building, just a woven steel curtain. If something did explode you wanted a path for the debris. On the outside of the building was a curved ramp, like a skateboard half-pipe. That way any explosion would be directed upward rather than outward.

My favourite chemical bunkers are the ones with a couple of feet deep gravel on the roof. So if there is an explosion, the resulting fire is smothered I assume.

Another Things I Won't Work With entry: "Sand Won't Save You This Time"

http://pipeline.corante.com/archives/2008/02/26/sand_wont_sa...

How to Blow Up Your Kitchen With Hydrogen Peroxide.

A few years ago, upon returning home after work, my my wife told me that her mother had blown blown up her kitchen but that she was OK. (My late mother-in-law was a wonderful person BTW.)

I can be prone to inattention when my wife speaks to me but this, this got my attention. :-)

My mother in law was an antique dealer. To restore/bleach old china, she would put some (hair dresser grade) hydrogen peroxide in in/on the china in question and let it warm in the oven.

One day she did this, but for some reason, this time she used her kitchen microwave instead of the oven. While it was warming she stepped out of her kitchen (to put something in the recycle I think) and luckily escaped the blast that blew out her kitchen window and sent her microwave into the Great Beyond.

When the fire department came she, I guess, feigned ignorance of what could have caused it. She was after all, a sweet old lady.

After my wife finished telling me the story, I mentioned something to the effect that "You realize they used hydrogen peroxide in the German V2 rockets?"

A picture of the remains of the destroyed microwave was displayed at her funeral.

R.I.P. ma

Skimming comments before reading them all as I usually do it was hard not to notice the second last sentence in your comment: "A picture of the remains of the destroyed microwave was displayed at her funeral."

Certainly reddit /r/nocontext material.

That is really cool.

Any chemists care to comment on why the peroxide would explode in the microwave but not the oven?

http://ieeexplore.ieee.org/xpl/login.jsp?tp=&arnumber=166634...

These guy tested the decomposition of hydrogen peroxide across a range of microwave frequencies.

Since hydrogen peroxide decomposes when heated, I'm guessing it's just due to the microwaves heating the mixture.

microwaves are at the wavelength that 'excites' / 'wobbles' / 'resonates' (pick your analogy of ball and spring physics) the O-H bond. H2O is entirely O-H bonds (give or take) and hence microwaves heat food vicariously via the water in it (heating up day old rice from the fridge is easier/better if you put a few mL of water in it). Peroxide peroxide is H-O-O-H so plenty of O-H bonds to excite and hence decompose...

This is a wonderful series that (rightfully) gets posted here a lot. I'd like to point out that the author's blog is also worth digging into for interesting and insightful posts about the modern pharmaceutical industry. For example: http://pipeline.corante.com/archives/2012/03/08/erooms_law.p... (how knowing more has actually made us worse at finding effective drugs).

Indeed. Be sure to click through: http://pipeline.corante.com/archives/things_i_wont_work_with...

This is very bad advice if you have anything else you need to do today.

On the other hand, It Might Just Save Your Life!

... though one hopes that if you were planning on doing anything for which that would save your life that you'd already have a good idea of just how likely your day was to be spent dodging rapidly moving glassware. But hey, great lede for my little reply here, right? If this programming thing ever gets old maybe I can get a job writing the 11 o'clock news.

This guy is by far the funniest blogger I know of, I regularly and literally shed tears laughing at his "things I won't work with" blog.

And at the same freaking time he writes great thought-provoking posts about the serious stuff. Amazing.

I came here to say that fluorine is even scarier in some ways. Sure enough he's covered it: http://pipeline.corante.com/archives/2008/02/26/sand_wont_sa.... I really wish he was my chem professor back in school.

Speaking of Oxygen though, I once attended a lecture/Q&A by the Myth Busters. It was pretty cool, and during the Q&A portion someone asked "Is there a myth you started, and then backed out?". They said that they won't do anything with liquid oxygen. They had a few myths about it, did some research, and realized that it can set pavement on fire. They then decided not to proceed.

That's nasty, but my favorite florene compound is still the apply named FOOF also known as "Satan's kimchi".

http://pipeline.corante.com/archives/2010/02/23/things_i_won...

"And yes, what happens next is just what you think happens: you run a mixture of oxygen and fluorine through a 700-degree-heating block. "Oh, no you don't," is the common reaction of most chemists to that proposal"

"When 0.2 (mL) of liquid 02F2 was added to 0.5 (mL) of liquid CH4 at 90°K., a violent explosion occurred."

I mean how can't you love a substance that will violently detonate things at -180C.

I wonder why the author is so caustic in regard to hydrogen peroxide.

Here - http://yarchive.net/space/rocket/fuels/peroxide.html - second message mentions Clark's "Ignition!" facts, and in first Henry Spencer states:

While there are some storage headaches -- the stuff decomposes slowly no matter what you do, so you must provide for tank venting -- otherwise peroxide is much easier and safer to handle. Its bad reputation is half outright myth and half the result of 1940s experience with seriously impure peroxide. To quote a friend, a rocket-propulsion professional, who investigated the matter as part of a study some years ago:

"As far as we could find out, the stories about problems with peroxide were just that, stories... Peroxide, now, seems to only very rarely do anything exciting, at all. And, even then, it seems to never do many of the things attributed to it in the stories."

Of course hydrogen peroxide can be dangerous - relatively recent explosion in Sweden (peroxidepropulsion.com) reminds us about that. At the same time significant volumes of it with more than 70% concentration are routinely used - so a chemist can calibrate the feeling.

As a former-chemist, I can attest that oxidizers in general are pretty concerning.

You are correct that hydrogen peroxide (even up to 70%) is pretty safe by itself, but a chemist like Derek Lowe would use hydrogen peroxide in a reaction. Since he's an organic chemist, nearly every reaction is going to involve adding that oxidizer to a reducing agent (almost every organic molecule out there). When you add an oxidizer to a reducing agent, you're creating an unstable mixture that would love to explode. Just because it hasn't exploded on people in the past, doesn't mean it won't in the future.

I can remember doing some really stupid things when I was in grad school. I had a create pure m-CPBA [1] for a reaction (great! an oxidizer and reducing agent all in one molecule!!). Thinking I was smart, I purified a a lot of it, like 20 g (smart folks only purify what they need, like 1 or 2 g). To make sure it was dry I put it on a vacuum pump and then heated the flask with a heat gun. Nothing happened, but looking back I was dam lucky it didn't explode. If it had, I likely would have been seriously injured.

[1] http://en.wikipedia.org/wiki/Meta-Chloroperoxybenzoic_acid

I realize i barely know anything in chemistry. I have zero practical knowledge and would be almost incapable of performing any kind of chemistry exercise anymore ( yet i do have a scientific background).

Anyone here could recommend a book or a serie of books to get myself into shape on that subject ?

my sincere advice (as an ex-chemist) is - don't. i suspect you'll want to do something 'fun' and 'fun chemistry' can go very bad, very quick. go fast and break things has never, never been a motto in a chemistry lab (even the dragon tail stories in the manhattan project were despite advice to the contrary).

most of a senior/PG chemistry degree is about learning how to work with this stuff and it's not book learnin' so much as translating what should happen, into what could happen and then what shouldn't ever ever ever happen. this is best done in a practical mentor-tutor fashion. even saying that, most uni's are really crap at protecting their chemistry students. I damn near killed myself _after_ getting my PhD and didn't really learn how to analyse the risks until i worked in industry (which leveraged 8+ years of theory)...

It is a bit frustrating to read this when you lack the necessary intuition. Why is a bond strong or weak, what do these atoms want to bond with and how is this all related to stuff blowing up?

This is exactly why chemistry is so interesting and the ways in which things can combine is also why it is so difficult.

Fundamentally, it's mostly about the electron charges on an atom which are balanced out by the number of protons in the nucleus. The proton however is a tightly packed point charge but the electrons can only exist in various energy levels (think of different shapes) around it.

You could think of it as trying to pack a bunch of magnets that have very elaborate electromagnetic field shapes into a box in a specific configuration. You might find one configuration that happens to be 'stable' until a big piece of iron is nearby and then suddenly it all snaps into a new configuration.

The science background expected is pretty high. Some things are hard to understand without the background, but in this case it is pretty easy. Explosive chemicals have bonds between the atoms that are under a lot of stress (think of it like a wound up elastic band). An explosion occurs when the stressed bond breaks (the elastic band is let go). A chemical like the one discussed has several bonds that are under massive stress (i.e the elastic band is huge and wound very tight). All it takes is the slightest bump or even a dirty look and the whole thing goes boom!

That's actually very incorrect.

Bond breakage is ALWAYS endothermic. http://books.google.com/books?id=ZOm8L9oCwLMC&pg=PA202&lpg=P...

Edit: Sorry, I hate leaving one-sentence rebuttals.

The energy required to break the bonds are so low that in comparison, the energy released when the products of the reaction are formed is very high. This giant disparity in energy released at the same time creates a sharp increase of heat and light (boom).

Also, your company is pretty neat. Any way for me to directly contact you?

Of course what I am explaining is incorrect, but I am trying to give the GP an idea of what is going on. Using my elastic band analogy, releasing the band requires energy (it is endothermic), but it get across the idea that there is a great deal of potential energy stored that is released once the band is released (i.e. a small amount of energy put into breaking a very weak bond will, after all the chemical rearrangements, release a lot of energy).

Sure if you want to get in contact with me just write to any of the contact emails on my companies website - it will get to me in the end :)

If you want a pretty good layman understanding of chemistry I recommend this video series. It is high paced and a little silly at times but it keeps your attention and you can rewind anything you do not understand or miss.

https://www.youtube.com/watch?v=FSyAehMdpyI&list=PL8dPuuaLjX...

I will attempt at conveying my simplistic understanding of it (physics major here): electrons are negative, protons are positive. Electrons want to be matched with protons. Two atoms can form a strong bond if they have just enough electrons to bond them but not enough to repel each other. Oxygen can bond to oxygen via a double covalent bond (http://www.chemguide.co.uk/atoms/bonding/doublebonds.html) but it has too many electrons, so it is essentially on the brink of breaking up (much more so, than say H2O or CO2). Basically, if you have an unstable oxygen bond, many things introduced nearby can disturb it, starting a reaction.

The rest is easy: a single atom of Oxygen is extremely reactive. If you take an O=O molecule (= means double covalent bond) and add some fuel, you get fire. At high concentrations, drop in just a bit of fuel and you can get a violent reaction.

Urg, O2 is actually a very bad example, because it's actually 'O-O' (where the ticks are radicals), this is called "triplet" oxygen. In the ground state it's a single bonded O2 with two free, unpaired electrons. There is "singlet" oxygen which is typically depicted as O=O, but it's actually O triple-bond O with two antibonding electrons that negate one of the 'triple' bonds which makes it effectively O=O but very different in reality.

If the OP asks about Newton's laws, and the parent responds with a brief summary of F=ma and friends, what good does it do to launch into a discourse about how all that stuff is totally wrong in the context of Lorentzian spacetime?

99% of physics and chemistry education consists of learning that whatever they taught you last semester wasn't quite right.

Let me try my hand at simply explaining this.

Atoms are composed to two sections:

A positively charged center -- the nucleus.

A negatively charged outside -- the electron cloud.

When several atoms get together, they do so because their electron clouds start intermingling. This sharing of their electrons is fundamentally what a bond is.

A bond is strong when both of the atoms really want their electrons to intermingle. Conversely, a weak bond is when the atoms are "forced" to be next to each other and intermingle. Strong bond = opposite poles of a magnet next to each other. Weak bond = similar poles of a magnet next to each other.

Somewhat counterintuitively, it's not the fact that the bond's want to separate from each other that makes something really explosive/reactive.

To really understand what's going on, you have to take a look at the energetics (thermodynamics) of how a reaction proceeds. The tendency of the physical world is always towards disorder (entropy). Rather than becoming more ordered, every single atom in the universe wants to be more comfortable.

Think back to our magnet analogy. Magnets with the same pole facing each other really don't want to be next to each other. In fact, they'd LOVE to find another magnet with the opposite pole facing them. The magnets which have a weak bond find it really, really easy to separate. In fact, almost anything will split the connection. However, those magnets, once separated, must find another (opposite) partner for them to pair up with. The amount of energy that they release when they find their perfect mate is evidenced by the fact that the magnets will literally hop across short distances and smack together in a satisfying *crack.

What we also know in thermodynamics is that energy cannot be created, nor destroyed. Thus the net energy in any reaction must be equal on both sides. We know a couple of things:

The energy required to split the weak bond is really, really little.

The energy released when a strong bond is formed is a lot (in fact, you hear the release of energy in the form of heat and sound!).

Atoms prefer strong bonds to weak ones (entropy).

Putting everything together, when you have an molecule with extremely weak bonds (HOOOH), it takes almost no effort for those bonds to come apart. However, when those oxygens go find other molecules to bond with, that releases some energy. Thus NET ENERGY is heavily favored in the exothermic (release of energy) direction. When enough of those super weak bonds are broken, and when enough of the strong bonds are formed rapidly, you have a simultaneous release of a huge amount of heat --- an explosion.

Sorry if that's a little long, but I tried to explain your questions. (Which was a fundamentally very interesting question!)

I found this super helpful. Thank you very much for taking the time to write it.

it's actually got a lot of problems with it. Preferring strong bonds to weak ones is enthalpy. Entropy is (roughly) "preferring to make m product molecules over n molecules when m > n because the combinatorics of their positions is bigger"

Energy is the total sum of the Entropic and Enthalpic components. (entropy takes a negative sign because more entropy is preferred; less enthalpy is preferred)

The text also doesn't explain what makes for high vs low energy. I'll try to explain this.

An electron is a wave. Two rules to remember: 1) a wave has higher energy when it has more nodes. 2) electrons have higher energy when it spends time 'away' from positive charge. The shapes of these waves are constrained by quantum mechanical rules, but generally speaking a 'higher energy' bond has either more nodes or has more density away from the nuclei.

You're certainly correct.

I was just attempting to keep it simple.

yeah, I'm usually pretty good at explaining things simply, but none of the explanations here are making me happy, and I can't come up with a good explanation that encapsulates my intuition. Perhaps that means that I don't actually understand it very well myself.

I'm always amazed at the hazardous chemistry that some labs do! They are obviously taking the necessary precautions, but I'm not sure I'd have the guts to do it.

I worked as a chemist for 7 years and witnessed 4 serious accidents, 3 of the 4 due to oxidizing agents (2 of them were peroxides). Some of the folks have scars to this day because of it.

Actually this happens in lots of scientific fields - microbiologist and virologists work with dangerous pathogens, physicists with radiation, etc. I think people underestimate how much danger there can be in the lab if you want to do research.

Well, at least chemical reactions fall into the "fail early and loudly" category. You know something is wrong.

Radioactivity and virus work strikes me as possibly more dangerous because of the relatively silent nature of the failures.

No, some chemical reactions fail early and loudly.

For absolutely no explosive lulz at all you could try for an exciting career in organic mercury compounds. (But first, I'd recommend checking out the wikipedia entry for Karen Wetterhahn: http://en.wikipedia.org/wiki/Karen_Wetterhahn )

Or, did I say "no explosive lulz"? Apparently at one point the USAF considered using dimethyl mercury as a rocket fuel. (Source: buried in "Ignition: an informal history of liquid rocket propellants" by John D. Clarke, which can be found here: http://library.sciencemadness.org/library/books/ignition.pdf )

True Charlie, I should have said most of the time...

The Wetterhahn case was mentioned in the original comment thread (or one of the articles linked from the original post) and was so shocking that permanent changes in regulations and practice occurred.

More mundane and work-a-day 'early failures' here...

http://pipeline.corante.com/archives/2012/02/16/when_reagent...

PS: Posting this from near the site of a biological failure that claimed two lives and (I gather) inspired one novel...

https://en.wikipedia.org/wiki/Janet_Parker

Derek’s blog is one of the best blog’s I have read. If you want to learn about the pharmaceutical industry and how the process of drug discovery really works (or doesn’t work) then I recommend it highly.

On topic I wouldn’t want to work with peroxide peroxides either :) Derek often has write up about what some of the really crazy organic chemists who work on unstable compounds do - truly eye opening for someone with a biology background like me.

Agreed. My favorite is still any post discussing Flouride bonds, particularly FOOF

http://pipeline.corante.com/archives/2010/02/23/things_i_won...

Yes you have to love working with something that can set sand on fire!

I wonder if anyone ever did order 1 kg of the stuff.

Fluorine can be so dramatic.

I witnessed a test of a small (500 lb thrust) H2/F2 rocket engine. The fuel & oxidizer were fed into the combustion chamber with small turbo pumps, which was the point of the test. The native fluoride protective coating failed in the F2 turbo pump, and there was an explosion with subsequent metal/fluorine fire.

Blockhouse sealed off and we all grabbed the Scott packs as a yellowish cloud of fluorine drifted by, setting fire to sagebrush as it went. Can't beat exotic propellants for excitement.

I'm intrigued: what's a Scott pack? Is is just breathing apparatus? But since the gas cloud is setting organic matter on fire surely you'd need more than that?

Or is it just a good pair of running shoes?

Scott makes a variety of Self Contained Breathing Apparatus (SCBA) devices. Mostly you see them used by fire-fighters, but Scott offers chemical industry and oil and gas variants. Check out their SCBA offerings here: https://www.scottsafety.com/en/us/Pages/ProductSeries.aspx?P...

I'm with you on needing more than that: anecdotally I was once advised to use an air filter plus nose clip in case of any accidental releases. I asked "Uh, like what?" "Oh, ammonia, that sort of thing." Needless to say if ammonia was released and it got to me I'd be blind anyway. :shrug: So based on entirely anecdotal experience I'd say yeah it's to hopefully help you run away. :-)

I've been told that some criminals like to keep ammonia in a squeeze bottle (like a jif lemon container) to be used as a weapon if necessary. Also handy that they can use it to clean their cocaine as well.

My favorite is Hexanitrohexaazaisowurtzitane...

"There's a recent report of a method to make a more stable form of it, by mixing it with TNT. Yes, this is an example of something that becomes less explosive as a one-to-one cocrystal with TNT."

http://pipeline.corante.com/archives/2011/11/11/things_i_won...

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