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Things I Won’t Work With: Peroxide Peroxides (2014) (blogs.sciencemag.org)
215 points by rishabhd on Aug 4, 2016 | hide | past | favorite | 102 comments


If you've not had the pleasure, take some time this weekend to read John D Clark's amazing book Ignition!

https://library.sciencemadness.org/library/books/ignition.pd... (PDF may not render properly in Chrome)


If you enjoy "Things I Won't Work With" and "Ignition!", I would also recommend the book "Excuse Me Sir, Would You Like to Buy a Kilo of Isopropyl Bromide?". It can be found online rather easily but I'm unsure of the copyright situation.


I loved the dry humor in it. I generally find chemistry boring, but this book was not at all boring, though it was all about chemistry.


It would have been nice if someone had linked me to that while I was still in HS, though I couldn't take both the tech path and the chemistry class; would have been wonderful.


Chemistry is a fascinating subject, people who don't like it become that way mostly because of terrible teachers, it's also my own experience. If you study chemistry on your own you will find it's much more fun and useful for understanding the world, many aspects of our whole modern society exists thanks to chemistry, i wish more people opened their eyes to it.

Here are some fun podcasts to listen: http://www.rsc.org/chemistryworld/podcasts/


I have a theory that everyone who studies chemistry is some kind of pyromaniac.


I always say that there are only two real specializations in chemistry - pyrotechnics and drug manufacturing.


no there are also future 'illegal substances' manufacturers ;)


It's a fantastic read, and the term "Hard Start" is one I've used a couple of times when engines have lunched themselves, usually leading to an explanation of where the term came from a and a difficult sell on trying to get someone to read the book - no-one else I've spoken to has, and they've really missed out!


I've been reading it for some time, but it's taking me forever because I often find that I want a deeper understanding of what he's talking about: what's this molecule composition again? What are its bounds? Why is it more fragile anyway? How does redox works again?

I think it needs to be read with a BSc chemistry class cheat-sheet of some sort, which I haven't found yet. Anyone knows any dense, crystal-clear chemistry 101 ressource on the web?

Edit: grammar.


It makes it clear that "rocket science" is not actually about Newton's laws, but about incredibly evil chemistry.


It's also about creating machines with the minimum possible safety margin added. And huge machines, by the way.

It's also about assembling huge teams, and yet keeping all their data in secret.

It's also about extremely reliable electronics/software that must survive on the some of the last hospitable environments available, but must not ever get any maintenance.

It's about a huge set of incredibly hard problems. Every one fascinating.


Wow. What a gem. Loved the humor and the science. Thanks for the pointer!


I think this is my favorite of the series: http://blogs.sciencemag.org/pipeline/archives/2008/02/26/san...


This comment is awesome:

Ah, the old sand bucket. Was out in the hall outside the undergraduate labs. Might have been there since benzene was linear. Top was decorated with cigarette butts, dried gum, bits of paper. Then one day down the hall the THF still is being cleaned out – long over due. Thick clumps of whatever ketyl becomes. Inside, a bright shiny prize of sodium metal that disagrees with the optimistic and impatient grad student’s use of straight ethanol as cleaning aid. Fire erupts. Extinguished by CO2. Humid day, icy glass, beads of water form and follow gravity down. Into and onto sodium metal. Fire erupts. Extinguished by CO2. Repeat several times until it dawns that CO2 will eventually run out. Send terrified lab mate down the hall to fetch savior: sand bucket! Weight of bucket: about 200 lbs. Skinny grad student risks hernia rushing it back to lab, arrives exhausted, collapses in victory like Pheidippides. Firefighting grad student drops damned CO2 tank, plunges bare hand into sand bucket. Screams in pain – sand has been accreted by age into protoconcrete, impermeable to human flesh, spatulae, metal rulers, etc. Fire meanwhile burns itself out. Sand bucket replaced for next sucker.


I'm a big fan of http://blogs.sciencemag.org/pipeline/archives/2010/02/23/thi..., if only for the call-out of a chemical supplier that claims to sell the stuff by the buttload.

Second favorite goes to http://blogs.sciencemag.org/pipeline/archives/2006/05/30/thi..., if only for the phrase "I’d like to shake the hand of whoever determined that property, assuming he has one left."


My favorite: "I’d call for all the chemists who’ve ever worked with a hexanitro compound to raise their hands, but that might be assuming too much about the limb-to-chemist ratio."

from: http://blogs.sciencemag.org/pipeline/archives/2011/11/11/thi...


That one has my favorite chemistry quote:

    At seven hundred freaking degrees, fluorine starts to 
    dissociate into monoatomic radicals, thereby losing its 
    gentle and forgiving nature.


Fluorine is in almost every chemistry joke. That's not a good sign if you need to handle it.


The same guy also prepared O4F2 (FOOOOF) and made it react with ozone (http://www.nrcresearchpress.com/doi/pdf/10.1139/v66-221):

> At 116 K (melting point of Freon-12), tetraoxygen difluoride decomposes and, if there is contact with concentrated ozone, both explode.

No shit Sherlock. :)

Strangely enough, I cannot find any paper about Streng doing explosive reactions with O3F2.


Another candidate for best quote is in his article on ozone products:

> In general, we chemists shy away from compounds with lots of single bonds between the elements on the right-hand side of the periodic table. Those guys tend to have a lot of electron density on them, and bonding between them is a careful, arm’s-length affair, sort of like porcupines mating.


interesting fact: a butt is an actual unit of measurement, so there really is such a thing as a buttload.

https://en.wikipedia.org/wiki/Butt_(unit)


My favorite line, "FOOF is Satan's kimchi."


You've got to respect something that will burn stuff that's already burnt.


That's a line I will use in the future. Well done.


I was hoping it was Sand Won't Save You This Time and was not dissappointed.


Yup, that's how I found this guy's blog the first time.

http://blogs.sciencemag.org/pipeline/archives/2008/02/26/san...


much more difficult to handle than fluorine gas


There are things that we shouln't work with, but we do because we don't know the associated risk, some examples:

  -maintenance of your DOT4 brakes? do not touch the DOT4
   brake fuild, it's absorbed though your skin and it will
   kill your kidneys when they try to filter it.
  -Old house in america? check you don't have any pipe 
   soldered with lead, hot water will eventually make it 
   evaporate
  -lead in electrical solder wire
  -mercury, a powerful neuro-toxin
Edit:

  -again, old house, check to change the paint, yep, lead
   in the pain again.
  -close to an airport? beside noise, lead in the airplanes 
   fuel
  -Teflon... again Dupont and 3M
  -Aluminum on cookware... toxic
lead was one of the technical debts introduced by a guy (1)... the same guy who introduce it to the fuel making a generation at least 10 iq point less smart.... and created the CFCs in aerosol... Dupont, GM and others did a lot of money on that.... as always.

(1) https://en.wikipedia.org/wiki/Thomas_Midgley,_Jr.


1) DOT4 doesn't exactly jump through the skin-- it's no dimethylmercury, or even DMSO. Its MSDS recommends against "prolonged" skin contact. It's not much worse than any other common hydrocarbon solvent, like gasoline. http://www.brake-eng.com/global/downloads/dot4fl%20dot%204%2...

2.) Hot water certainly doesn't "evaporate" lead-- lead's boiling point is 1700C. Hot water can leach lead from solder joints, if your water isn't treated properly: https://www.epa.gov/ground-water-and-drinking-water/basic-in...

3.) Yeah, lead solder isn't great to spend a lot of time with, which is why RoHS was introduced in 2003: https://en.wikipedia.org/wiki/Restriction_of_Hazardous_Subst...

4.) Where are you going to find bulk metallic mercury in any house built in the last three decades?

5.) Lead paint was also phased out years ago.

6.) Leaded avgas does still exist, and is bad. Don't buy property near airports that fly small planes.

7.) Teflon is about as chemically inert as a flororcarbon can possibly be. You might be thinking of Perfluorooctanoic acid, which is involved in Teflon production, and is pretty nasty: https://en.wikipedia.org/wiki/Perfluorooctanoic_acid

8.) Aluminum cookware isn't toxic, are you nuts?


A house older than three decades, but there was an interesting story (previously discussed on Hacker News) about some poor guy unexpectedly finding a huge lump, probably left over from an old heating system.

https://news.ycombinator.com/item?id=10357115


Not a lump; it's liquid anyway. Lots of tiny droplets under our floor: http://www.jefftk.com/mercury-under-floor-2x.jpg


I never heard of aluminum being toxic to any extent, but a quick search showed this

http://www.nytimes.com/health/guides/nutrition/cooking-utens...

> Aluminum cookware is very popular. Nonstick, scratch-resistant anodized aluminum cookware is a good choice. The hard surface is easy to clean. It is sealed so aluminum cannot get into food.

> There have been concerns in the past that aluminum cookware increases the risk for Alzheimer's disease. The Alzheimer's Association reports that using aluminum cookware is not a major risk for the disease.

> Uncoated aluminum cookware is a greater risk. This type of cookware can easily melt. It can cause burns if it gets too hot. Still, research has shown that the amount of aluminum this cookware leaches into food from is very small.

Not sure what "sealed" aluminum is nor what it would be coated with to prevent any kind of leaking. This is all new to me.


Aluminum exposed to air very quickly grows a thin passive layer of aluminum oxide (unlike steel rust, this layer is stable). Anodizing forces it to grow a thicker layer.

Aluminum oxide is hard stuff: 9 on the Mohs hardness scale (talc = 1, diamond = 10). https://en.wikipedia.org/wiki/Mohs_scale_of_mineral_hardness


Also note that pure crystalline aluminum oxide is called corundum, or when doped with other elements, the precious gemstones ruby and sapphire, rocks of exceptional hardness and chemical resistance.


> chemical resistance

I remember from a freshman chem lab that trying to dissolve aluminum into acid doesn't work because acid promotes oxide growth, so we dissolved it in NaOH, which was supposed to attack the oxide, then acidified the solution. Are the aluminum oxide minerals similarly susceptible, or do they also resist alkali?


While we're issuing corrections...

> Hot water can leech lead from solder joints,

It's leach


Fixed. What a wonderful quirk of English, that both words mean mostly the same thing, but one is an animal, while the other is a verb.



> it's no dimethylmercury, or even DMSO

Skimmed an article on the latter…

“DMSO has the unusual property that many individuals perceive a garlic-like taste in the mouth after contact with the skin.” — Darn. Wasn’t quite sure things like these are possible.

“DMSO can cause contaminants, toxins, and medicines to be absorbed through the skin.”

“In Australia it is listed as a schedule 4 poison, and a company has been prosecuted for adding it to products as a preservative.” — What about other countries?! China?

Overall, the kind of information that I wish I didn’t have to know. Useful, but now I’m left to wonder what else am I blissfully unaware of.

By the way, what about fuel used in modern fighter jets (military industry is known for environmental tradeoffs), anyone knows if byproducts are harmful to those on the ground? Trying to figure out whether noise is the only issue with living by an military base with low-flying fighters every day.


> 5.) Lead paint was also phased out years ago.

And yet, as recent news reminded us, there's still plenty of it in Baltimore:

http://fivethirtyeight.com/features/baltimores-toxic-legacy-...


Seems like once a year or so I read something about attempts to replace good old 100LL avgas but we're still using it :-/


What's wrong with lead in solder? I wash my hands after soldering every time and I can't imagine how I'm really exposed otherwise. Professionals who solder long periods every day are far more likely to have adverse health outcomes from inadequately vented flux fumes.


There's nothing wrong with lead in solder. It's not going anywhere. The vapor pressure of lead at soldering temperatures is essentially zero, and in solid form it's about as bioavailable as neon.

As far as disposal is concerned, one car battery has more lead in it than every electronic device you'll ever own, but for some reason nobody cares about those.

(Yes, most car batteries get recycled... and that would have been straightforward and sensible to mandate for the rest of the world's lead-bearing electronics, compared to the nightmare that is/was RoHS.)


The most affected by lead are the kids, also the relationship to IQ decrease happens on infancy.


Oh cool, so I can be even more blase than I am.


As I understand it, the main issue with lead is disposal.


I think what the RoHS people really wanted to do was shut down lead smelters, which are nasty enough in themselves. They just used a nuclear weapon where a BB gun would have sufficed, and were indiscriminate about their choice of targets.

As far as disposal goes, there is some concern about lead in CRTs and solder leaching its way down into the water table and back up to our taps, but no one has ever demonstrated exactly how that happens to my satisfaction. I'll concede the point that it's best not to throw it away.


A mechanism that I don't even think was anticipated by the RoHS people, was that electronic waste was being shipped to third world countries, e.g., Europe to Africa, where people were burning the circuit boards in open air (perhaps assisted by kerosene) to collect and sell the metals.


Avgas is leaded petrol (gasoline in the US), used in reciprocating piston engines. That is, small planes.

(You might also find it in wankel or rotary compression/combustion engines, though those are rare.)

Gas turbines, which you'll find on major airliners and many propellor craft (turboprops) burn what's effectively kerosene.

The lead is added to petrol to avoid knocking, a problem where you're compressing fuel in a cylinder (or again, compression-rotary engine). It's not used in most commercial aviation.

Yes, if there are small craft flying out of your commercial airport, you'll have some lead exposure. But it's your small and personal craft that are the bigger concern.

(As with several other cautions here, the advice you're giving is incomplete, misleading, or in several cases, simply wrong. Lead in paint and plumbing, yes. Mercury, yes. Teflon? Maybe. Aluminium? No.)


-lead in electrical solder wire As pointed out by other contributors, lead in electrical solder is not a big risk with appropriate handling (i.e. wash your hands) I've been soldering as a hobbyist since my teens and hand had lead blood levels checked (see below) with no issue. Fumes from Rosin are a far greater risk and is a known cause of industrial asthma.

A much bigger risk of lead exposure is your local rifle range, esp. down range (i.e. the backboards / target area's)

Anecdotal warning TBH, but I meet a guy running an air rifle club and who also ran several other clubs up-to large bore shooting, and had been diagnosed with lead poisoning. He was also a re-loader, but blamed down range exposure.


> A much bigger risk of lead exposure is your local rifle range, esp. down range (i.e. the backboards / target area's)

I would guess instantly fatal levels of exposure, if you hang around at the target area during a shoot...


There is that. :)

But is true that the CDC lists shooting firearms (target shooting) as the #1 non-occupational source of elevated blood lead levels. http://www.cdc.gov/mmwr/preview/mmwrhtml/mm6025a2.htm#tab

(It is certainly preventable with proper procedure -- https://www.cdc.gov/niosh/docs/2009-136/pdfs/2009-136.pdf -- but I guess some operators are not aware of the risks, unfortunately.)

Lead in solder doesn't even make the CDC's table.


Pretty sure the lead in solder is not a huge concern for occasional random use. Wash your hands and don't breath the fumes...


Pretty sure metallic mercury isn't that toxic unless you inhale the vapors. Mercury salts or organomercury compounds are MUCH more toxic.

Pretty sure DOT4 brake fluid isn't that toxic.


Mercury is different because it does emit vapors at usual temperature ranges. Very little vapor, but long term exposition can be damaging, even if you don't ever touch it.


The fumes don't contain lead as it has a very high boiling point. The flux can be in the fumes though, which can be harmful.


Most of those things are exaggerated risks without context.

For example, from the MSDS for DOT-4 brake fluid:

Skin Contact: May cause irritation. Brake fluid may be slowly absorbed through the skin. Excessive exposure for extended periods of time involving large areas of skin would be necessary for absorption of harmful amounts.


I still wear the "extreme" nitrile gloves from Harbor Freight (black, 9mil), a P100 respirator, and safety goggles when working with it or doing any car maintenance. Who knows what other nasties are in all that road grime.


And note that the same brake fluid is also used in push bikes, if they have hydraulic disk brake setups.


Hmm, I have hydraulic brakes on a one of my bicycles, Shimano Saints, and they use mineral oil... not generally considered too risky to have in contact with skin.


Aluminum on cookware? A lot of cookware is aluminum in most professional kitchens..


So it seems...

http://whfoods.org/genpage.php?tname=dailytip&dbid=92

Seems like the gold standard of cookware it's cast iron.


> This metal has consistently been placed in the top 200 health-jeopardizing toxins by the ATSDR (Agency for Toxic Substances and Disease Registry) at the U.S. Department of Health and Human Services.

So if we look at the list at https://www.atsdr.cdc.gov/spl/ it says:

> It should be noted that this priority list is not a list of "most toxic" substances, but rather a prioritization of substances based on a combination of their frequency, toxicity, and potential for human exposure at NPL sites.

The list also contains other metals as copper or silver.

If you actually read their profile about aluminium it's mostly about inhalation of aluminium dust (who is surprised that inhaling metal dust destroys your lungs?), aluminium buildup in people with kidney diseases (also not too surprising that all kind of stuff builds up in your body if your kidneys don't work anymore), and chemical compounds that contain aluminium e.g. antacids and buffered aspirin.

The only really interesting thing in there is the link with alzheimer's disease.

> Another neurological effect that has been proposed to be associated with aluminum exposure is Alzheimer’s disease. Although a possible association was proposed over 40 years ago, this association is still highly controversial and there is little consensus regarding current evidence. A number of studies have found weak associations between living in areas with elevated aluminum levels in drinking water and an increased risk (or prevalence) of Alzheimer’s disease; other studies have not found significant associations. In contrast, no significant associations have been found between tea consumption or antacid use and the risk of Alzheimer’s disease; although the levels of aluminum in tea and antacids are very high compared to drinking water, aluminum from these sources is poorly absorbed. The available data do not suggest that aluminum is a causative agent of Alzheimer’s disease; however, it is possible that it may play a role in the disease development.

Oh and they also found neurotoxicity in animals if they were fed ridiculous amounts of aluminium.


Wow. TIL the same man was responsible for CFC refrigerants and tetraethyl lead in gasoline.


Check out how he died.



I never tire of seeing this series reposted. I only wish he'd written more since 2014.


There is probably only so much he won't work with.


Why chain-mail gloves? I guess it would react with plastic gloves, but wouldn't some peroxide get through the gaps in the chain-mail?


With chain-mail gloves, there's a decent chance you still have hands after the explosion.


Chainmail strikes me as more useful for kinetic than chemical protection.

E.g., when the experiment blows up in your hands (or near them).


I think the primary purpose is to keep the hot glass shards from shredding your skin. I'm guessing you wear standard rubber/plastic gloves underneath the chainmail to protect against the heat and chemicals.


I'm also curious. If the peroxide explodes, a layer of chain mail could protect against cuts from the shrapnel, I suppose?


I'm guessing, but since in other contexts metals are used as a catalyst to decompose HOOH I suspect that it protects your hands from direct exposure. This would release a lot of heat, but that's likely better for you.


isn't that the joke...? It wouldn't do anything to help but "Part of the purpose, I believe, was to make you think very carefully about what you were doing as you put them on"


Well, at least it keeps your hand in one piece for the surgeons to reattach.


Several of his articles mention chain mail gloves. I'm curious how those would protect you from chemicals, since chain mail is obviously quite porous. Or are they just meant to protect you from shrapnel when the container explodes in your hands?

(I also recalled my father demonstrating to me, at a young age, how a candle flame wouldn't penetrate screen-door mesh, presumably because the metal is conductive; and wondered if mail might perhaps give some fire protection similarly, by spreading the heat thin. That seems unlikely, though.)


Yes, the chain mail protects you from the experiment detonation products, such as fragments of blast shield or fume hood, lacerating your hands. Also recommended is an iron face-mask and heavy leather apron.

The candle effect you mention, is the principle behind Sir Humphry Day's safety lamp, as used by miners, which used a wire gauze screen to prevent flames igniting other flammable gases in the mine atmosphere. See https://en.wikipedia.org/wiki/Davy_lamp for more information.


I was calling in an order for some Acetic Acid one day and the lady asked "Glacial?"

I said, "Well, I think I'd like it a little faster than that."


He mentions the Me-163, which used peroxide. A fuel leak would dissolve the pilot.


It is more probable that the pilot would be violently redistributed in the atmosphere.


Yeah I doubt it used oxidizer to refrigerate the cabin so an averaging of the pilot/atmosphere ratio seems more likely than a dissolution oxidizer leak[0]. And it would probably set the pilot on fire rather than dissolve it:

> Because of its extreme oxidizing potential, T-Stoff was a very dangerous chemical to handle, so special rubberized suits were required when working with it, as it would react with most cloth, leather, or other combustible material and cause it to spontaneously combust.

At 57% methanol and 30% hydrazine hydrate (by weight), the reductant wasn't exactly innocuous either.

[0] even more so as the reductant and oxidizer were picked for their hypergolic combination, ground explosion is not unheard of for 163.


That happened a lot, too. (I read a book on the 163.) The Me-163 killed many more Luftwaffe pilots than Allied.


I'm finding the peroxide-ozone as suggested wastewater treatment an interesting suggestion. Any further soures on that?


A web search found http://www.calpoly.edu/~ceenve/enve/jsczechowski/enve436/pro... .

> Based on these results the use of the UV/Ozone/Peroxide, especially the modified UV/Peroxide system, proved an effective process for removing and containing VOC contamination in the groundwater. The system was designed to treat 30,000 m g/l and the average influent was 25,00 m g/l. Along with the high contaminant removal, the system design conditions were met. The modified UV/Peroxide process replaced the UV/Ozone/Peroxide system, because the initial system, containing ozone, required lots of maintenance on the ozone generator and the delivery system. Ozone leaks were discovered (causing downtime) and the residual ozone proved to be corrosive in the reaction chamber.

This supports the description that Lowe gave.

https://duckduckgo.com/?q=UV%2FOZONE%2FPEROXIDE+TREATMENT&t=... seems to be a fruitful search term.


Thanks. I did see that earlier.

More toxics / contaminants remediation than sewage treatment. Might be interesting to see if it could break down, e.g., dioxins.


I wonder if somebody has done similar posts (as well written and humorous) on "Code I won't work with".


http://thedailywtf.com/ would count as "Code I've been forced to work with".


This are some cool unventilated kitchen experiments involving leather, sugar, flour and 99% hydrogen peroxide: https://www.youtube.com/watch?v=i06SnRCQN6U


"High-concentration hydrogen peroxide was formerly available in 70, 90, and 98% concentrations in sizes of 1-gallon, 30-gallon, and bulk-tanker truck volumes."

From the HTP Wikipedia page.

I grew up 3 houses from I-40. I'm surprised I'm alive.


(2014)

Entertaining, as always.


"Instead of being locked in a self-storage unit with two rabid wolverines, why not three?"


For me, hydroflouric acid.


Is Corante no more?


Dr Lowe moved everything from Corante to Science including the archives. Not too long ago. Corante was having too many technical problems.


This is a fun 2 minutes if you enjoyed that blog. https://www.youtube.com/watch?v=u6MfZbCvPCw


After this publication I shall use this sequence O-O as my favourite emoticon. Or oxygenicon.


Hooh?


No seriously, what is the author intending to say that when repeatedly putting it between sentences.


It's a fairly common informal way of writing the chemical formula (H2O2) that tries to be a little more faithful to the geometry of the molecule...

so HOOOH is hydrogen perperoxide, literally a chain of three oxygen atoms with a hydrogen atom at either end. In my electrochem (Chem 2) class, the instructor used to sometimes write HOH for water.


He isn't putting it between sentences. It's part of what he's saying. HOOH is hydrogen peroxide, also sometimes written H2O2. HOOOH is dihydrogen trioxide / hydrogen perperoxide.




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