
Things I Won't Work With: Peroxide Peroxides - joe_bleau
http://pipeline.corante.com/archives/2014/10/10/things_i_wont_work_with_peroxide_peroxides.php
======
ChuckMcM
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.

~~~
Danieru
How? How!?

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

~~~
ChuckMcM
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.

~~~
gregpilling
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.

------
mikeyouse
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.

~~~
refurb
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.

~~~
keithpeter
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.

~~~
arethuza
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...](http://pipeline.corante.com/archives/2008/02/26/sand_wont_save_you_this_time.php)

------
chrisbennet
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

~~~
ajb
That is really cool.

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

~~~
refurb
[http://ieeexplore.ieee.org/xpl/login.jsp?tp=&arnumber=166634...](http://ieeexplore.ieee.org/xpl/login.jsp?tp=&arnumber=1666345&url=http%3A%2F%2Fieeexplore.ieee.org%2Fiel5%2F11051%2F34864%2F01666345.pdf%3Farnumber%3D1666345)

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.

------
idlewords
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...](http://pipeline.corante.com/archives/2012/03/08/erooms_law.php)
(how knowing more has actually made us worse at finding effective drugs).

~~~
jerf
Indeed. Be sure to click through:
[http://pipeline.corante.com/archives/things_i_wont_work_with...](http://pipeline.corante.com/archives/things_i_wont_work_with/)

~~~
CamperBob2
This is very bad advice if you have anything else you need to do today.

~~~
jerf
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.

------
IgorPartola
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...](http://pipeline.corante.com/archives/2008/02/26/sand_wont_save_you_this_time.php).
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.

~~~
Retric
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...](http://pipeline.corante.com/archives/2010/02/23/things_i_wont_work_with_dioxygen_difluoride.php)

"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.

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

Here -
[http://yarchive.net/space/rocket/fuels/peroxide.html](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.

~~~
refurb
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](http://en.wikipedia.org/wiki/Meta-
Chloroperoxybenzoic_acid)

------
bsaul
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 ?

~~~
jgamman
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)...

------
revelation
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?

~~~
nathannecro
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!)

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

~~~
dnautics
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.

~~~
nathannecro
You're certainly correct.

I was just attempting to keep it simple.

~~~
dnautics
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.

------
refurb
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.

~~~
keithpeter
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.

~~~
cstross
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](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](http://library.sciencemadness.org/library/books/ignition.pdf)
)

~~~
keithpeter
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...](http://pipeline.corante.com/archives/2012/02/16/when_reagents_attack.php#comments)

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](https://en.wikipedia.org/wiki/Janet_Parker)

------
danieltillett
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.

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

[http://pipeline.corante.com/archives/2010/02/23/things_i_won...](http://pipeline.corante.com/archives/2010/02/23/things_i_wont_work_with_dioxygen_difluoride.php)

~~~
ridgeguy
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.

~~~
Robin_Message
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?

~~~
technofiend
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...](https://www.scottsafety.com/en/us/Pages/ProductSeries.aspx?ProductType=d0mFzhYO7R8=)

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. :-)

~~~
petemc_
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.

