Sciencemadness Discussion Board - Had an acciedent.......

Had an acciedent.......

Polverone - 4-9-2002 at 13:04

Sometimes, no matter how smart you think you are, you can be a moron. Last night I discovered that a plastic bottle that holds concentrated sulfuric acid for an hour won't necessarily hold it for three hours. I now have a wooden shelf with extensive acid damage, one coat that looks like it was attacked by radioactive killer moths, a discolored plastic tabletop, and several blackened patches of carpet (mixed with sodium carbonate that still needs to be vacuumed up). Oh, and a discolored streak running down one wall. It could have been worse. If I'd spent any longer eating supper it could have spread to engulf my computer and hotplate before I noticed. And it could have been a lot better, if I'd set the bottle inside a glass dish like I thought about doing.

Rhadon - 4-9-2002 at 13:20

I didn't think that sulfuric acid could attack plastics! Do you know what kind of plastic it was? How much sulfuric acid was in the container?

And you have your computer near to your chemicals? Fumes can harm the sensitive components inside. This reminds me of my time in school... a TV in one of the chemistry rooms had be be replaced because it was defect. The reason was corrosion caused by vapour of corrosive substances or vapour that forms corrosive substances in contact with water (such as SO₂).

Plastic unknown

Polverone - 4-9-2002 at 13:43

Until yesterday I didn't think that any common acid (including sulfuric) would attack plastics either. I don't know what sort of plastic it was; the bottom of the bottle holds the recycling code that tells what type it is, and it was destroyed. The bottle was originally used to hold sterile eye drops for use with contact lenses. I thought it would make a nice dropper bottle for small amounts of H2SO4 indoors (since I store the big jug outside in a cabinet). I came into my room and thought things smelled a little funny, but I was doing a reaction on the hotplate so I didn't think too much of it. Then I saw over on my shelf that there was a puddle of acid formed, and a thin stream falling on the table below the shelf. The acid was coming from the bottom of the bottle that I had set there.

When I tried to pick up the bottle to put it in a glass pan to take outside, the whole bottom fell away (that's when the acid went down the wall and onto the carpet). If I'd been thinking a little better I would have set the glass pan up to catch the acid instead of trying to move the bottle. But, of course, many things could have gone better (or worse) yesterday.

I am not too worried about vapors from this incident damaging computer equipment. I do think that my monitor is suffering progressive failure from exposure to various fumes, though. I was aware of the potential problems but this monitor has lasted several years and has a big scratch on the screen (from careless handling by someone moving it) anyhow.

There were probably 300-400 mL of acid in the bottle at the time of the incident.

madscientist - 4-9-2002 at 13:53

I have removed the metal needle from plastic syringes in the past to use them to slowly dropper sulfuric acid into reactions. Those syringes were ruined.

vulture - 5-9-2002 at 07:54

The danger with sulfuric acid is that one quickly forgets that its solution is just strongly acidic, but in conc. form it is actually a strong oxidizer.
Most plastics are degraded by strong oxidizing acids, think of HNO3.

PE, for example, resist dilute and strong acids, but not strong oxidizing acids. PP resists it limitedly.

PHILOU Zrealone - 8-9-2002 at 09:55

Don't be surprised, the same happened to me with HClO4 70% in a 500ml PET bottle! It stayed OK for 4 days and when I took the bottle same as what happened to you happened to me!Hopefully I recollected 80% of my precious liquid with some damages to the synthetic carpet, my desk and school bag.
Funny to see how 70% HClO4 can virtually chew paper...it becomes transparent and liquid like glue...it also becomes extremely unstable owing to spontaneously burning/explosive organic esters of HClO4...man that burns fiercely with explosions!

So plastic is indeed corroded by acids (especially oxydising ones).
Depends on the plastic nature, molecule, charge (sometimes inert, sometimes not).
Polyesters and polyamides are destroyed by bases and acids (hydrolysis) PET (polyethylene terephtalate is one example).
Metacrylate is destroyed by oxydisers and by the sun owing to reactive double links.
Rubber is destroyed by oxydisers (cf double links).
PE restist acids and oxydisers but the caps often dont.
Polystyrene doesn't resist oxydisers!
PVC doesn't resist long acids and bases and oxydisers.
Teflon resists all!

So it is wise when you play with acids to store them in glass bottles with PE caps or glass rod caps...sole exception is HF that corrodes glass ;-)!

Xenos - 13-9-2002 at 15:04

Somewhat off topic, but i thought id post this anyway... A few days ago, my friend was pouring some H2SO4 into a glass test tube, and spilled some down his hand. Not willing to take a nice acid scar down his fingers, he intelligently puts the test tube down on my wooden table and washes of his hand. Well i noticed the 10ml of acid spilling onto my table, and quickly fixed the problem. Anyway, now there is a nice bare spot, free of the paint drips and laquer spots.

Terphthalate Plastic

PrimoPyro - 17-9-2002 at 03:42

H2SO4 definitely eats certain plastics, it all depends on which kind. Terphthalate plastics (like common soda bottles) are simply polyesters, and are easily hydrolyzed by acids and bases as well.

Sorry to hear about the mishap Polverone.

PrimoPyro

daryl - 21-9-2002 at 05:38

My act of stupido was to attempt to heat some ruthenium oxide in a stream of hydrogen.

The hydrogen was generated by dissolving zinc in HCl. The H2 was passed throgh a dreschel bottle of H2SO4 to dry it. The exhaust tube has some steel wool to prevent blowback.

The stupido was that the zinc was from old batteries and had some MnO attached to it. This reacts with HCl to produce chlorine. Therefore I was heating a mixture of hydrogen and chlorine and passing it over a red hot metal oxide. The gaseous mixture exploded, destroying most of my glassware and throwing the tube from the dreschel bottle onto the roof of the family car.

The H2SO4 dissolved the duco down to the bare metal before I found it and concealed it from my father with house paint.

I was wearing goggles at the time and I managed to remove the HCl from the concrete floor and most of the H2SO4 from the car

trinitrotoluene - 1-12-2002 at 13:50

Some common plastics do resist strong acids. When I bought a liter of 31% HCl its in a HDPE bottle. The 93% H2SO4 I bought was also in a HDPE bottle.

lucifer - 1-12-2002 at 15:44

A friend of mine stored 58% HNO3 in a plastic Coca-Cola bottle.
After one year he picked it up and the bottle broke in lots of pieces,
The carpet was now soaked with HNO3 acid and dark brown fumes (NO2) came from the hot carpet.
He of coarse had to through away the carpet.

My cautionary tale

trinitrotoluene - 1-12-2002 at 18:55

It was yesterday when i've opened up 2 instent cold packs. I thought both or them was NH4NO3 but 1 of the packs, the substance was colored yellow which was kind of strange.But both was laden with moisture.I was planning to dry both of them and store it in a soda bottle. The first pack which i'm sure was NH4NO3 because its white and has the same properties as pure NH4NO3.I poured the prills into a beaker with a handle, placed it on a hot plate turned on low.After most of the moisture is gone I then poured it into a soda bottle for storage.The second pack was colored yellow. I did the same as i did with the first pack, place it into a beaker and heated it on low. But as I heated it, it gave off a very strong oder. The oder was the smell of very strong ammonia.I then tured off the heat and evacuated the area.I then turned on the computer went on aim to ask a few questions. The answar I got back was the yellow substance in fact wasn't NH4NO3 but was Urea. But the person also said the fumes could be ammonia or hydrazine. But later on it was determined that it was ammonia not hydrazine. Infinatly better. But so far that was the most that happand to me.

KABOOOM(pyrojustforfun) - 7-12-2002 at 18:43

I see every body is admiting accidents

. this is a warning that there is always some thing we don't know that hurts us. 5 mounths ago I concentrated some H₂SO₄ (with unknown concentration) to 95-98% (by heating).it was in a 500 ml balloon and had a rubber stopper with 2 holes, one for the thermometer the other hole had a shaped glass tube inside which was led in a bottle ful of water to prevent harmful fumes (although it was outside). I heated it to above 300°C(don't remember the exact temp) I stopped heating and waited for some hours then pulled the glass tube and pushed a piece of plastic bag through the hole and poured some candle drops on it to seal the hole, at this time it was around 80°C.
some days later I saw beneath of the balloon was sucked in sulfuric acid and some of it was spreaded on the table, fortunately it was glass. I could save 300 ml of it. and covered the place with sodium carbonate. there was a scratch in the balloon. I think when it was cooled it made a vacuum pressure that caused the problem.

PET

notagod - 8-12-2002 at 05:30

PET plastic, at least the one found in bottles here in Sweden, are in fact very resistant to acids and bases. To hydrolyses it you need to boil it in ethanol and KOH. (Of course it will somewhat get attacked by acid and base, but not much)

Beat this...

Ramiel - 12-12-2002 at 23:30

I accidentally made Potassium nitrousamine (which is really carcenogenic), and then inhaled a great lungfull of it...

Life expectancy = Life expectancy - 40

Running for my life

trinitrotoluene - 13-12-2002 at 22:24

Last sunday I decided to make some chlorine gas. So I mixed 100ml of 31% HCl with 100 grams of Calcium Hypochlorate which is 75% and has 78% avaliable Chlorine.I did this outside. This is what I did. I took a 20 oz soda bottle filled it with the HCl then made a paper funnel and added to Calcium Hypochlorate. My plan is for it to react slowly and I will close the cap trapping the Cl gas.But it reacted very quickly and vigerously I also underestimated the volume of Cl gas it will gererate. Then I was overwhelmed with Cl gas and a stream of yellowish green gas shot up out of the bottle. Without a gas mask I am doomed as i'm choking on the gas. I then held my breath and made a run for it. I had escaped. To calm my self down I decided to take a walk around the block. As i wa a block away I can still smell Cl gas.Can not beleave its so strong. As I hear dogs barking everywhere maybe because of the smell. But for now I learned my lesson and I will get a gas mask. But a few things i have to say, never unestimate the power of chlorine!

explosion

trinitrotoluene - 8-3-2003 at 22:11

Today I mixed 20 grams of sucrose with 30 grams of KNO3 both finely powdered. Placed it into a copper cruciple. And heated it on a hotplate. I found a stick outside so I used that one to stirr. When the stuff started melting some KNO3/sucrose go stuck on the stick. So I decided to place the stick on the heating element of the hotplate. The stuff ignited and I raised up the stick while its still burning vigerously. A spark or something went off and went into the 50 grams mixture. Boom....... a large cloud of smoke and molten stuff sparyed everywhere. 2 feet away I can see holes burned through soda bottles. And around the site on my deck, burned indentations are on the wood. My paints have holes burned in it as well as my jacket. My face dosese't seem to be affected thay seemed to miss me face. The only exposed area was my face and hand. On my wrist I suffered some 2nd degree burns which are quite painful. After this I learned a lesson. I'm not going to fool around nomore.

Chlorine

blindreeper - 11-3-2003 at 03:56

Well I had an accident with chlorine and went to hospital beat that TNT lol.

I was making it with HCl and KMnO4 and it wasn't going fast enough and added to much HCl. But why would any one what to make Cl2? Cause copper spontaniously combusts when in contact with it cool!!!

DDTea - 11-3-2003 at 16:55

Interesting... I've made Chlorine many many times and breathed it in each time. However, I've never had to make any hospital visits...just take a few hours to relax and be calm after exposure. It's almost a fun process now, to get to know my chemical creations so well

. Of course, there are some chemicals I would never think of trying this with!

In fact, the best "Right-Now" treatment for almost any gas inhalation (Save for the ones that attack skin and eyes, causing terrible burns), is plain fresh air! I would hesitate to make any emergency calls concerning an accident in my lab...but I assume you made a suitable excuse, that you had a "cleaning accident"

. How badly were you exposed to your Chlorine though?

PHILOU Zrealone - 13-3-2003 at 03:13

I have had a long time ago when I was young:
*2 toxic gases emission in my house (Cl2 and NxOy)- I had to go out and leave my appartement with open windows for 2 hours and take fresh air!
*2 explosions; one on my balcony while attempting to make benzyl chloride from toluen, hypochlorite, HCl and sunlight; another one with an explosive homemade firework that I wasn't able to use for New year (it was one of 10 devices) but owing to temperature (-26°C) I had no more gaseous gas to light the fuse and my fingers were frozen), I had already enjoyed 9. The device detonated in my room when I wasn't there! Explosions always cost a lot when you have to repair or replace carpets, windows, mirrors, wallpapers,furnitures!(roughly 1000 $ + crazy screaming angry mother).
*A strong hand burning from a homemade hand grenade based on glycerol/KMnO4 and black powder.Hopefully I cured very well owing to good personnal medical skills.
*Two hot acid spills on the carpet and vinyl cover of my room (total cost of replacement 600$).

From this I learned a lot:
*Never store mix of chemicals!
*Never keep ready to use explosive device!Always use fast!
*Always use soft PE container instead of glass, metal ones!Schrappnels!
*Make a decent lab, your room or kitchen aren't labs...all damages will go to your house, or parents house!
*Always use safety fuse.
*Think to consequences of a possible explosion (endanger neightbourgs, walkers, brothers, childrens, parents; destroys a room, furniture, set fire to other devices or chems).
*Keep it small and dismantelled (small is always safer than large one).
*For dangerous experiments allways outdoor, never indoor!
*Outside damages cost much less than inside ones!
*Store reactive chemicals far away from each other!
*Store explosive chemicals outside!
*Learn as much as possible about any experiment and hazards!
*Understand the chemistry behind it!
*Never add an extra ingredient to a safe mix without thinking four times about the possible side reactions!

Ramiel - 15-4-2003 at 20:01

Quote:

Originally posted by PHILOU Zrealone
Polyesters and polyamides are destroyed by bases and acids (hydrolysis)

It has been my experience that polyethylene terephthalate (PET, PETE; plastic coke bottles for example) is resistant to acids such as HCl.

er, I don't understand why you might say that then 'PZ. (not meaning to be rude!)

I will look into converting my storage from PETE to PE though! I don't want my lab to end up like yours Polverone!

madscientist - 15-4-2003 at 22:22

If you want a real mess, try dissolving nickel alloys in an aqueous solution of ~25% Caro's acid. It's a nuisance to clean up the solution of nickel salts that's ejected from the reaction vessel - consider their toxic nature!

Cappy - 21-4-2003 at 21:02

I can't find chemical resistance information for saran plastic and paraffin. I was specifically interested in their resistance to H2SO4 (up to 50% or so concentration).

There's a good chem. resistance file on the FTP. It lists the resistance TO many chemicals, but not OF many chemicals.

PHILOU Zrealone - 29-4-2003 at 05:10

I have had PET bottles:
*with diluted HNO3 and H2SO4; after one year it visibly has shrinked in size and hardens; some crakels are visible and acid spills observable...bottle start to decompose as multilayers.

*with concentrated 98% H2SO4, 70% HClO4, 70% HNO3 bottle melt/liquefy and becomes glueish after a few days

*with NH4OH (20% NH3) bottle opacify upon time and starts to pelliculate plastic layers inside within a few monthes bottle is reduced to puzzle size brittle fragments.

Following this I say, ON PURPOSE, that HCl 35% bw will do the same and thet PET bottles aren't suitable for chemicals storage!

The molecular formula of PET will make you understand this:
-(CH2)n-O2C-C6H4-CO2-(CH2)x-
with n,x= k*2 (k real integer between 1 and 100)
The acid will free some HO2C-C6H4-CO2H and
HO-(CH2)x-OH or HO-(CH2)n-OH breaking the plastic fiber integrity; a base will do the same but also cristallise the terephtalate salt inside the polymer matrix and yield the opacity and flakes.

Parafin is alkanic and looks pretty much like PE except that owing to a lower molecular weight (or chain lenght) Parafin (from latin parum affinum -little affinity (to react)) will be more soft, brittle, less elastic and display a lower melting point.

Saran is some kind of polyester or polyamide (I think some kind of Nylon); nylon doesn't stand acids oxydising ones being the worst with imediate decomposition (HNO3 or HClO4 70% make it melt on contact ... ever put some hairs in HNO3- hairs are polyamides (polypeptides based on serine (from "soieries";silk in french) it foams and vanish in a nasty soup in a day!).
It may stand a little longer (a few days with strong nonoxydating acids/bases) but not that much!

JustMe - 7-8-2003 at 14:49

Wow, I just discovered this site. And I thought that I was alone in the chemical craziness of my youth. Although I never lost interest, it fell by the wayside. And I may later start some threads on some topics worth taking up by some other mad home scientist.

Anyway, as for my blunders (30 or more years ago)...

1) Never store liquid butane in a glass jar at room temperature. Sure, it's only a couple of atmospheres, but eventually the glass just gives up and goes boom.

2) A little more than a "classic"... durn foolish. If I remember correctly, Potassium Dichromate, Salt and Sulfuric Acid heated together yields Chromyl Chloride. It's a really neat substance. Dark red, like bromine... and a powerful oxidizing agent. I was considering it as a rocket fuel oxidizer and then thought better of it. I had a brick wall and put a small petri dish containing a few ml (!) of it on the other side. Carefully I let a few drops of anhydrous alcohol fall into the dish. Woosh! Instant flames! Only THEN came the mistake. Tossed water on it. Chromyl Chloride is violently decomposed by water too! Bigger flame! But, as I said... brick wall! Thank goodness for that!

3) Never was courageous enough to handle cyanide... instead I made Hydrogen Selenide. Later learned it is 20X more poisonous than the former. Ack!!!

4) Heated Kaolin clay with concentrated Sulfuric Acid as part of an attempt to find a way to bring aluminum into solution. The resulting fumes required that an entire wing of my high school be evacuated.

5) Nitrogen Triodide... enough said!

Y'know, it's amazing I survived my youth!

I think I'll stop now before I really look like an idiot. But I think the concept behind this BBS is cool. I'll check in now and again. My hope too, is that there will be some chemistry student here I can interest in picking up a study I started a long time ago. It had great potential... the prof thought I had found a new type of chemical bond (and I've never seen any research in this area since), but due to circumstances beyond my control, I couldn't finish the research. Ah well. Cheers

blip - 7-8-2003 at 18:31

I once attempted distillation of MEK from nail polish remover in my microwave.

After about 10 minutes on and off the glass bowl I used to condense the gas exploded and was heard a room away. Apparently it got superheated and shot out of the "boiler" cup so fast that it split the thing in half and splattered it all over my microwave. It's a turned out to be good cleaner and I knew the risks, but I'm so f'ing lucky it didn't combust.

I'm not gonna take risks like that anymore!

Quote:

My hope too, is that there will be some chemistry student here I can interest in picking up a study I started a long time ago. It had great potential... the prof thought I had found a new type of chemical bond (and I've never seen any research in this area since), but due to circumstances beyond my control, I couldn't finish the research. Ah well. Cheers

Interesting, please explain.

Ramiel - 7-8-2003 at 23:02

I usually pride myself on my clean glassware, but after trying to boil a few solutions that superheated... well, let us just say that there is such a thing as a healthy ammount of grime.

[edit - spelink]

[Edited on 8-8-2003 by Ramiel]

JustMe - 8-8-2003 at 08:36

Well, its off topic, of course, Blip... and I'm going on vacation tomorrow... so I'll just give an overview of the class of compounds I was studying.

My study involved Saccharin (yes, the sweetener), which is actually an interesting compound structurally. I was synthesizing transition element saccharin salts with the premise that saccharin could act as a chelating agent (i.e. form coordination compounds) with same elements. This would mean a new class of coordinating compounds not seen before.

So I prepared Saccharin salts of Copper (II and I), Cobalt (II), Iron (II), Manganese (II), Zinc, Nickel, Silver and even Palladium (interesting yellow cubic crystals on the last one). One piece of evidence in favor of my hypothesis was that Copper Saccharin dissolved in Acetone to form a deep green solution from which green crystals slowly separate, resembling Cupric Acetate. If you look up the structure for this acetate, two copper ions are bound by acetate bridges and I believe that Saccharin was doing something similar.

I found all sorts of neat chemistry going on, and I was able to grow large crystals of these salts.

Anyway, hope that answers your question. I may start another thread on this project only to see if I can interest somebody in picking up where I left off (in an academic venue)... or even just for fun if you can get the chemicals. Then I'll reveal some more of what I found out.

Cheers.

First experience with superheating

gritty_cryst - 8-8-2003 at 09:34

One balmy day I was recrystallizing an amine salt in IPA. I wanted to reduce the volume of solvent after the first flush of crystals so I decided to boil it off on a hotplate. I turned the hotplate on and left for a few minutes. I returned much later than I should have and was surprised to see that much solvent still remaining. I dropped in a stirbar and was taken aghast by a supersonic whoosh sound and the flooding of the area by IPA. Definitely preferable to a sulfuric acid spill though.

DCM will shrink common soda bottle plastic too. Although I don't know the chemistry behind it (does anyone?), DCM in a soda bottle for a few hours makes for an interesting souvenier.

Al Koholic - 29-9-2003 at 18:35

Thick walled wine bottle + too much HCl + too much Al foil + plastic tubing of too small a diameter leading into a wash bottle = BOOM in your hand.

Had an acciedent.......

trichomegrower - 23-10-2003 at 18:21

hi guys, i just thought i better tell you this to warn some of the less experienced about this. About a month ago i made about 80g of AP, the standard way with sulfuric. I have made it many times b4 with only one accident that could have been more serious (left AP in sun, detonated, blew concrete throught neigbours window...) So here i was with 80g, and decided to make some small detonaters. I used 1 inch copper tubes. I seperated probably about 1g AP and put it on a piece if paper, wich i was going to use to pour the shit into the tube. As i poured the stuff in, the friction in between the crystals and the paper caused by the ap running down into the tube, detonated. Luckily i was wearing a full face mask, thick clothing and industraial goves. I got 7 stiches on the side of my hip, from which they reomved a tiny but of copper, and 2nd degree burn to most of my palm and front if fingers. I am so lucky i did not lose any finger or have more serious burns. Ater this i quit dealing with AP after experiencing first hand, just how sensitive this shit can be.
BE CAREFUL, it may just save your life.....

drat

Polverone - 23-10-2003 at 19:02

It appears that malicious raccoons wrote part of the board software, because when I tried to merge this message with the thread "A cautionary tale" in Miscellaneous, XMB managed to totally screw up the old thread.

Anyway trichomegrower, if you're posting on a subject that already has a thread - like accidents we've had - please post in that thread.

[Edited on 10-24-2003 by Polverone]

DarkVigilante - 23-10-2003 at 20:42

Well, I won't berate you as you obviously learned your lesson. Sorry you got hurt. Just remember people, hundreds of chemists smarter than you or I have been killed screwing around. So, if you don't want to die then don't make large amounts of these sensitive compounds. I know we all believe we are safe, but as you can see this field often leaves no room for error. Hell, most of the guys who died making these compounds died after years of experience. Sometimes we just need to be satisfied by only testing a little of the product. If you are in this game just for the thrills then sooner or later you are going to take a spill.

trichomegrower - 24-10-2003 at 03:21

yes, very well said. I could have easily died as i was very much considering just loading all of it into a bottle and blowing it to hell, but "luckily" changed my mind. Who else has ever made AP that is that sensitive? what does it usually take for it to detonate? such as, pouring into a container, touch it, putting in sun, slightly heating etc.

Incidents with HMTD

chemoleo - 24-10-2003 at 05:56

Did anyone ever have similar incidents with HMTD, i.e. unpredictable detonation etc? Or does anyone know someone who had?
In my experience, it always was very stable, and would not detonate by flame, it'd just deflagrate. Else it needs a hard, well-aimed hammer blow. Friction never seemed a problem, I tested it with very small amounts. THe only way I managed to set it off reliably, without confinement, was with a small amount of thermite...

Backyard Blaster - 24-10-2003 at 06:01

Yowtch! Good thing you were wearing safety gear, or else you might be lacking a couple of senses.....
Makes me a bit more nervous about AP, for sure. I've made tons of it over the years, even using it for detonators, and haven't had any such accidents.
Drying in the sun doesn't sound like a good idea. I've always dried mine in a cool, shady area, and I never use any kind of heat source to accelerate the process. I often test for impact and friction sensitivity, and it always seems to pass. The only reason I can think of, for your accident, is perhaps there was a high level of acid remaining in the product. Also, you didn't specify which acid you used; most literature I've read suggests that HCl yields a slightly less sensitive form of AP (dimeric).
Definately some food for thought there, and like many other posters/readers, I too would dump this stuff without a second thought, if I had access to a safer primary explosive.

vulture - 24-10-2003 at 08:25

Dimeric or trimeric depends on the temperature. Dimeric is LESS stable than trimeric!

If you are stupid and smash some conc H2SO4 into your reaction mix you'll get mostly dimeric because of the hydration heat.

DDTea - 24-10-2003 at 10:37

Heh, I had not even thought about the dangers of Acid + AP when I came up with the crazy idea of making Chloroacetone by AP + Hydrochloric Acid. Fortunately, that was just a post- not an actual experiment. I have had my eyes on AP for a while, but not with much longing to make. To me, I see it more as 4th of July fun...and as a detonator for ANNM

.

But you see, this is why I am afraid of explosives... They are too unpredictable for. The comparison has been made between them an a pet boa constrictor (I don't remember who made it, but it was very good): the boa constrictor has a one-track mind... He may love you all along, but then thinks, "gee, I like you so much I could just EAT you," and in line with the one-track mind, he does. The next day he thinks, "I sure miss that guy."

Explosives are the same way. Do not ever let yourself become complacent around something so unpredictable, and especially not as unstable as AP! As for me, I play the Violin and I use my hands a lot...I don't like the risk of losing fingers.

So, I will stick to my toxic materials- at least they are mildly predictable and won't explode on me

brite_lites - 24-10-2003 at 13:34

A guy in my class is now in the mater hospital in dublin (A Children's hospital for seriously ill children) after an incedent with HMTD. He has lost sight in one eye and is fighting for his life in intensive care. Please, think about the risks before making organic peroxides.

argh I really feel sorry for him

KABOOOM(pyrojustforfun) - 25-10-2003 at 19:07

we all know how powerful HMTD is please tell how the accident happend. HMTD is not even comparable with AP. it doesn't sublime thus doesn't grow its crystal size. at room T decomposition is negligible but accelerates with T rise.
<table border=1><tr>weight loss %</tr><tr><td>temperature<br>hour</td><td>60°C</td><td>75°C</td><td>100°C</td>< ;/tr><tr><td>2</td><td>0.10</td><td>0.25</td><td>3.25</td></tr><tr><td>8< ;/td><td>0.35</td><td>0.60</td><td>29.6</td></tr><tr><td>24</td><td>0.5</td> ;<td>7.3</td><td>68.0</td></tr><tr><td>48</td><td>0.5</td><td>2.25</td><td& gt;decomp smell</td></tr></table>
deflegration point is 200°C !! (for AP it's about 100°C). impact sensitivity is 30% lower than mercury fulminate. I think with the following notes dialing with HMTD becomes reasonably safe.
1. use atleast 30% H2O2 or higher concentrations (but not very high)
2. for acid catalyzer use citric acid
3. at the stage when you want to let the soln T rich to room T stir vigorously for some hours (till most crystalls form)
4. instead of neutralizing with bicarb soln just wash several times with tap water and a last time with distilled water then 2 times with ethanol
5. make sure it's "completely" dry before use
6. keep in dry, cool and dark places
7. use immediately (it stores well though)
8. NEVER mix HMTD with anything
9. the most reliable method I have seen is the one on megalomania's site. needless to say the proportion of chemicals, durations, temperature... are very important
note: 1, 2 & 3 have effect on crystall size of the batch and as a resut on impact sensitivity

chemoleo - 25-10-2003 at 19:54

Hmm, I just wondered how you judge reliability... for myself, I tend to take the data out of a book, or journal papers (simply because they wouldn't publish unless it was 100% reproducible). Always made HMTD according to COPAE, and never ever had a problem with it, and HMTD's properties were always reproducible

--> a scientist's dream!

[Edited on 26-10-2003 by chemoleo]

HMTD vs AP

chemistr1 - 6-11-2003 at 15:45

In my dreams I have stored HMTD for over 12 mnths. Also dream about making it by the kilo and I always end up with a 90-95% yield I have never had an accident yet and would never even dream about making AP as HMTD has always safely fitted the bill with no differences in batch and it can be plasticised with a little patience. Large crystals forming in AP differences in one batch from another, forget that

BromicAcid - 4-12-2003 at 20:45

I'm trying to finish up my list of accident's that I've had during the course of my chemistry adventures and I've added it to my web site. It's good for a laugh

http://members.aol.com/bromicacid/mistakes.htm

Polverone - 4-12-2003 at 20:57

That was truly an epic tale of phosphorus production gone wrong, at the end. Did you ever make it go right?

Theoretic - 5-12-2003 at 07:58

"Welcome to hell"... Indeed!
Anyway, have you used aluminium powder in excess and calcium phosphate?
Sodium phosphate would require much less heating to initiate, and bulk aluminium would be much more safer, the stochiometric amount wouldn't give aluminium phosphide (or so I think).
A tale of my own stupidity. It wasn't an accident, but it was stupid.
I made some thermite by wrapping anhydrous CuCl2 (the hydrated version said to decompose on heating, so dehydration is said to have be accomplished by heating in a stream of HCl gas... ...I heated it in a Pyrex flask over a candle

, dehydrated nicely to a brown powder, which is the colour of anhydrous CuCl2 , this gives us all a lesson - don't trust the textbooks!) in aluminium foil. Then I heated it over a candle

, IT IGNITED! it then burned with a brilliant white flame, and the stupid bit was that I was doing it INDOORS! The air filled with smoke, which I believe consisted of AlCl3 and Al2O3 - not healthy. I was holding it with tweezers - not even at arms length! Thank god the thing burned out before the flame reached the other end - the consequences for the tweezers would have been vile. I didn't think nothing of it at the time, though.

BromicAcid - 5-12-2003 at 11:23

Quote:

Anyway, have you used aluminium powder in excess and calcium phosphate?
Sodium phosphate would require much less heating to initiate, and bulk aluminium would be much more safer, the stochiometric amount wouldn't give aluminium phosphide (or so I think)

I used stoichimetric amounts according to the following reaction:

(NaPO3)6 + 10Al + 3SiO2 -----> 3Na2SiO3 + 5Al2O3 + 6P

Sodium hexametaphosphate was superior to other phosphates I have tried. Revisions of the reaction used straight aluminum powder where as the reaction I used in my mishap involved aluminum turnings with aluminum powder. Also, in further experimentation I used really fine sand (that I bought from chem supply company, fumed silica, 100 g was about .5 L in volume) and I improved my reaction vessel, put a screen over the end to diffuse bubbles and trap phosphorus from reaching the top. I plan to do more experimentation in the summer months, I will post detailed results when I get my yeild over 7%. I believe the aluminum phosphide was just because the reaction was nowhere near complete, if it went to completion it would have all been reacted away like you reconed.

Sulphuric acid

TomThumb - 22-9-2004 at 02:47

Iv discovered that using Sulphuric acid to make AP makes it more sensative. despite they tempature.

Stick to Hydrochloric, I dont know why but it makes a difference!

The_Davster - 22-9-2004 at 14:22

HCl evaporates off of the CTAP while sulfuric does not. So therefore when using sulfuric acid it stays on the crystalls which leads to increased sensitivity.

But a simple search could have solved your question on this.

AP

MadHatter - 25-9-2004 at 11:21

TomThumb, H2SO4 also tends to increase the heat of the reaction. Higher heat
favors the less stable dimeric form of AP. So you're right - stick to HCl.

lefty - 9-11-2004 at 07:02

Since you ask, I will relate to you my incident with HMTD, back when I was less interested in the "theoretical" and more in the "practical."

Was loading HTMD into empty .22 magnum casings using the TM-31-210 method (though not using the recommended safety equipment)

The contaminated casings, me being a little overzealous with packing pressure...possibly a few other factors contributed to the next few minutes of high drama, involving me with a dumfounded look on my face staring at a hole in the desk, wondering why my ears were buzzing and just where was all that blood coming from?

6 hours and 37 stitches later I was pretty much back to normal... except for the piece of metal that nearly took out my right eye. It's amazing what modern surgery is capable of - this was over 10 years ago though, so I'm sure the techniques have even improved since then.

I was lucky in that I survived and still have 10 fingers and 2 eyes, though the intraocular lens implant I needed to restore my vision kept me out of the military...the FBI... and a few other positions I aspired to later.

Ironically, I spend most of my day now reminding people to wear their eye-protection as an Industrial Safety Professional.

Life's a joker, no?

moonclub - 18-11-2004 at 11:11

organic peroxydes are really dangerous. no matter HMTD or AP. using of HCl is recommended. (10 green prods standing on the wall...)

Tetrameric AP is better

Tweenk - 7-12-2004 at 13:57

Quote:

Originally posted by trichomegrower
(..) I used 1 inch copper tubes. I seperated probably about 1g AP and put it on a piece if paper, wich i was going to use to pour the shit into the tube. As i poured the stuff in, the friction in between the crystals and the paper caused by the ap running down into the tube, detonated. (...)

I think not the friction was the case of detonation. Organic peroxides (dimeric AP especially...) decompose exothermically in contact with metals. So making AP blasting caps with copper tubes as the casings is basically a suicide. The fact you might have made the dimeric AP could also play the role. I'd reccomend you to make tetrameric acetone peroxide instead: To a solution of 1,5 g SnCl4 x 5H2O in 40 ml of 30% hydrogen peroxide add 40 ml of acetone. Stir the mixture for 24 hours with a stirrer or just let it to react on its own (at room temperature). Crystals will gradually form. After 24 h (or some more if you haven't stirred) cease stirring, evaporate off all the unreacted acetone (preferably with a water pump), filter off the solid, then recrystallise it form 50% acetone/water solution or benzene. You will get about 12 g of crystals that melt at 93*C without detonation and is stable even at 120*C.

i have never had an accident with AP

Hideki Matsumoto - 18-12-2004 at 09:26

I do find if you pack AP slightly moist into a sealed container made of thick cardboard you never have to worry about premature detonation. Metal conatiner idea is just not that smart!!!
second thing make sure you store all your AP charges in a cool dark environment properly labeled!!!!!
I did have someone throw a 200g APAN blasting charge into the neighbours bonfire one time in an old wooden crate.. duh... the result was a massive explosion and bits of wood and crap on fire raining out of the air for several 1000 ft!! The blast knocked down trees around the blast zone and windows around the neighbourhood.
Well someone easily could have been killed in this unfortunate situation, neighbour thought it was a full propane tank that went off. Awww..

IT SCARED THE SHIT OUT OF ME ! LABEL YOUR EXPLOSIVES SO THIS DOESN't HAPPEN TO YOU!

Polverone - 18-12-2004 at 13:13

Quote:

Originally posted by Hideki Matsumoto
I do find if you pack AP slightly moist into a sealed container made of thick cardboard you never have to worry about premature detonation. Metal conatiner idea is just not that smart!!!
second thing make sure you store all your AP charges in a cool dark environment properly labeled!!!!!
I did have someone throw a 200g APAN blasting charge into the neighbours bonfire one time in an old wooden crate.. duh... the result was a massive explosion and bits of wood and crap on fire raining out of the air for several 1000 ft!! The blast knocked down trees around the blast zone and windows around the neighbourhood.
Well someone easily could have been killed in this unfortunate situation, neighbour thought it was a full propane tank that went off. Awww..

IT SCARED THE SHIT OUT OF ME ! LABEL YOUR EXPLOSIVES SO THIS DOESN't HAPPEN TO YOU!

200 g of a mixture of ammonium nitrate and an organic peroxide knocked down multiple trees and hurled debris thousands of feet into the air? I think this story has grown a bit in the retelling.

Edit: stories like this also cast grave doubts on your credibility in reporting, for example, the successful synthesis of DPPP and exploration of its wondrous high-performance properties.

[Edited on 12-18-2004 by Polverone]

Polverone, DPPP has wonderfully high performance!!

Hideki Matsumoto - 18-12-2004 at 23:58

1# Yes, you are absoultly wrong Polverone! DPPP rivals all organic peroxides in power!! The patent is 100% correct about the detonation velocity. 9Km/sec
2# This ~200g 9 it may have been a bit more than that. -250g APAN charge story is true. It did some horrific damage due to the fact it was in a tightly packed wood/ metal crate. The force of the explosion was powerful enough to knock down a few trees , and scatter red hot coals all over the neighbourhood. I found hot embers and bits of wood about 2500ft away from the blast zone.
It looked like someone touched off a landmine... The crater that this charge made was about 1ft deep.
2 trees that were roughly 3" thick that were next to the fire ( 3ft away) were sheered from midline and snapped like twiggs.
Again I have pictures of the site to post.

neutrino - 19-12-2004 at 07:09

Quote:

Originally posted by Hideki Matsumoto
It did some horrific damage due to the fact it was in a tightly packed wood/ metal crate.

Obviously, you don't quite understand the difference between an LE and an HE. HEs don't need comfinement to explode violently. Your story somewhat reminds me of this lamer.

i know the difference between LE and HE thanx

Hideki Matsumoto - 19-12-2004 at 19:50

You are talking to a chemist here and one that is very well rounded in explosives thanx.
The crate did nothing really to contain any gases and one end happend to be opened on the case. I have tried exact (approximate) amount of APAN without extra containment. The result was a huge concussion and overpressure. I think the reason behind the 2 trees getting flattened were due to the flying case bits and ( metal sharpnel shards) ....
Wow... I just wished i had a video tape off this... I do have pics of the aftermath though. These are coming soon.
APAN is quite powerful stuff. ratio for my APAN is 56:44

I call Bullshit!!

Joeychemist - 19-12-2004 at 20:18

I too now believe you to be a ”bullshiter”. You say you’re a “chemist” and that you’re “very well rounded in explosives”. But you would throw 200-250g (which ever one it is we don’t know because you like to change you’re storey) in you’re neighbors fire. No chemist I know with half a brain would throw APAN in a steel crate into a fire. Let alone a chemist who is “well rounded in explosives”.

Wasn’t there shrapnel imbedded into you’re neighbors house.

You’re right though about one thing. APAN is very powerful, but not the mix you’re using. APAN is most powerful when the mix is between 8-15% AP and 92-85% Ammonium nitrate and requires a blasting cap to detonate. It would seem like you’re lying. maybe???

[Edited on 20-12-2004 by Joeychemist]

You aren't reading the previous 2 posts!!

Hideki Matsumoto - 19-12-2004 at 23:59

As I said, in the very begining, This was due to someone not reading the hazard sign on the box... BTW..I didn't throw it in the fire, just so you know.
The crate was made of wood, mostly with big metal reinforced sides. one side was partiially open as a vent. I AM NOT BULLSHITTING! I got in some serious shit from that incedent... ie) Police, I had to explain to the dumbshit who threw it in the fire that they could have KILLED someone. I guess danger labels don't mean shit to some people. i also had to pay my neighbour $$$ for new windows. There was some cosmetic damage to the house as well, but not to big a deal.
Luckily through all of this I wasn't charged! AS I SAID BEFORE NEVER LEAVE EXPLOSIVES IN UNMARKED CONTAINERS OR IN ACCESSIBLE AREAS OR THIS IS WHAT MAY HAPPEN TO YOU! ...
This true story is a reminder to those who make and store this stuff. Pictures are coming soon

Axt - 22-12-2004 at 02:36

Heh...

Heres some gems I found using a totally unrelated search on google.

Heres a variation on the APAN in the fire story.

Quote:

Hideki Matsumoto
ñ{ìñÇÃóùâ?ÇÕêSÇÃíÜÇ©ÇÁóàÇÈÅB (311 posts) 11-19-04, 10:11 PM
reply
Just to let you know how powerful both AP and DPPPD/DPPP are here is a story that will make everything very clear for you!

I was making a 50g blasting charge out of an open ended carboard tube 3/4" wide x 1" long. The material I was using was microcrystalline APAN that had been sitting for 2 months slow drying in a dark cool spot. i had a fuse in it ready to be use the day I needed it, and then something happend to it an I lost sight of it !!! The blasting charge went missing one day and ended up in a incinerator can to my discovery and to everyone in the neighbourhoods discovery !! It exploded !!! The incinerator can ripped open and the botton of it was blown into the air like someone dropped a hand grenade into it! The bast was so powerful that it shattered the concrete the incinerator was sitting on in a circular pattern.
The blast was heard 2miles away! luckily no broken windows or downed trees!

Quote:

Hideki Matsumoto
ñ{ìñÇÃóùâ?ÇÕêSÇÃíÜÇ©ÇÁóàÇÈÅB (311 posts) 11-20-04, 02:35 AM
reply
Yes, the only thing that was in the incinerator was the charge, if the whole vial container of APAN was in the incinerator (800g) I would have lost the side of my house and had bits of metal can wizzing around at 7500-8000m/sec taking out trees and windows and people for several 1000ft, I am sure. As I say again APAN is 250% more powerful than commercial Dynamite (TNT) and has a much higher det velocity. Had this been DPPP/DPPPD the situation would have been MUCH WORSE!

Wow, the "diamine" derivative goes all the way up to 9800m/s.

Quote:

Hideki Matsumoto
ñ{ìñÇÃóùâ?ÇÕêSÇÃíÜÇ©ÇÁóàÇÈÅB (311 posts) 11-15-04, 03:28 AM
reply
Another high order explosive that I have tried with sucess is D.P.P.P.D or D.P.P.P.
It is called chemically Dipherone Pentaperoxide (Diamine) and has the highest detonating velocity of all Organic peroxides at 9.8Km sec.

this is made my adding Acetone to HCL and heating it to around 40-50c the mixture turns green/yellow and smells pungent. leave this to sit/evapourate and collect the yellowish crystals from the residue after the precip has formed. This process is long 12-48hrs and needs careful inspection!!!

Add Hydrogen peroxide to the crstalline mass and chill immediatly in a freezer.
the end result is a greenish soild crystalline mass. Dry this out and it becomes an extreamly powerful heat sensitive explosive with a det velo of nearly that of PETN! BE CAREFUL WITH THIS STUFF AS IT IS ALSO HIGHLY TOXIC AND FRICTION SENSITIVE// DONT PUT IT IN A SCEW CAP CONTAINER OR IT WILL DETONATE!!

AP has 200% the power of TNT

Quote:

Hideki Matsumoto
ñ{ìñÇÃóùâ?ÇÕêSÇÃíÜÇ©ÇÁóàÇÈÅB (311 posts) 09-26-04, 01:21 PM
reply
How to make Tricycloacetone peroxide det Vel. 7600-8300m/sec:
Materials neeeded.

1)Acetone
2)35% HCL (Muratic acid) used as a catalyst.
3)30%-40% Hydrogen Peroxide (Hyperox) (Hydroponic sanitizer)
4) A refrigerator and ice bath to stabilize reaction.

I will tell you how to make this DANGEROUS HIGH EXPLOSIVE ! When dry it is highly sensitive to shock, metallic cmpounds, and heat. Light may even set it off.
Detonation power is 150-200% of TNT! It can be stabilized with Ammonium Nitrate but becomes hydroscopic if AN is added. The power factor is also increased.

Quote:

Hideki Matsumoto
ñ{ìñÇÃóùâ?ÇÕêSÇÃíÜÇ©ÇÁóàÇÈÅB (311 posts) 11-15-04, 03:05 AM
reply
I just made some of my own Dynamite !! yay!
I did a 60/40 with AP and AN/NM WOW !!! I got a det velocity over 8 Km/sec !!
I did blasting with the stuff!!
I use the best fuse on the market. Thermolite 5 metalized blasters fuse. burns underwater and in confined spaces $20CDN per 15m

And the best of all:

Quote:

Hideki Matsumoto
ñ{ìñÇÃóùâ?ÇÕêSÇÃíÜÇ©ÇÁóàÇÈÅB (311 posts) 11-23-04, 06:22 PM
reply
Just discussing Octonitrocubane and the power this molecule has with a contact of mine! Turns out that the military thinks that the detonation velocity of this compound could be in the neighbourhood of 91Km/sec (over sublight speeds). This would make this compund almost as powerful as a nuclear weapon! WoW the Cubane molecule has apparently 166KCal per mole of energy! I will see what I can come up with on how it is put together!

So much for your credibility Hideki et al. These are all extracts from http://www.sciforums.com

KemiRockarFett - 22-12-2004 at 02:55

I would like to tell you all, as you already known, that the density is needed to bee much higher to get so high VoD:s. That is nessesary for the shockwave to propagate fast through the matrix.
The person which claims this garbage is a mythoman.

Edit by C. removed massive quote.

[Edited on 23-12-2004 by chemoleo]

Good show man!

Joeychemist - 22-12-2004 at 02:59

Axt you finaly nailed this k3wl using his own lies against him. Great work man, I love it. I'm laughing so hard I'm allmost crying over here.

banned but welcome to return

Polverone - 22-12-2004 at 14:22

Hideki Matsumoto, if you are still reading this, feel free to register another screen name and get a fresh start. There's no vindictive streak here. You just need to keep your reports (outside of Whimsy, anyway) confined to reality.

MWRAY236466 - 12-6-2009 at 10:02

Hideki is right... DPPP is a very powerful HE. I did a recrystallization of the crystals that I got with this synthesis. I made a lot of dets. and the difference respect AP is really incredible... Dont try DPPP without a recrystallization. DPPP IS THE BEST PRIMARY EXPLOSIVE....

hissingnoise - 12-6-2009 at 10:24

Quote: Originally posted by MWRAY236466

DPPP IS THE BEST PRIMARY EXPLOSIVE....

Could someone please pass me the NaCl cellar. . .

User - 12-6-2009 at 10:49

Please tell me is this behavior contagious?

Years ago i had a small accident, and it scared the hell outta me.

A very tiny amount of 50/50 DS/MHN was placed in a small beaker and very gently mixed with a glass rod.
After stirring it as gently as possible .. it went off.
At least partially, it was still a bit damp and i guess that saved me.
Although it was a small amount (around 0.6-0.8 gram ) it could have done serious damage.
Still not absolutely positive about the cause, but i think it might have been friction or static electricity.
DS is not so insensitive as i thought.

I was lucky, and not planning to test this luck again.
My respect for high explosives keeps growing by the day.
I am no longer scared, just fascinated and respectful.
Habit is probably the biggest risk of them all.

hissingnoise - 13-6-2009 at 03:35

DS must be very sensitising but I can't find it on my virtual list of acronyms User; can you give us a reminder?

User - 13-6-2009 at 05:08

Sorry it's slang I guess

DS = double salts (referring to AgC2/AgNO3 )

edmo - 10-8-2009 at 02:33

My HNO3 is eating away at the plastic cap. Acids are so hungry.

PHILOU Zrealone - 31-8-2009 at 01:42

Quote: Originally posted by User

Years ago i had a small accident, and it scared the hell outta me.

A very tiny amount of 50/50 DS/MHN was placed in a small beaker and very gently mixed with a glass rod.
After stirring it as gently as possible .. it went off.
At least partially, it was still a bit damp and i guess that saved me.
Although it was a small amount (around 0.6-0.8 gram ) it could have done serious damage.
Still not absolutely positive about the cause, but i think it might have been friction or static electricity.
DS is not so insensitive as i thought.

I was lucky, and not planning to test this luck again.
My respect for high explosives keeps growing by the day.
I am no longer scared, just fascinated and respectful.
Habit is probably the biggest risk of them all.

Two factors might explain the explosion of your batch!
1°)The siver nitrate acetylide complex is a mix (clathrate) of silver acetylide, silver nitrate and nitric acid...
(x Ag2C2. y AgNO3. z HNO3)
AgNO3(aq) + C2H2(g) --> Ag2C2(s) + 2 HNO3(aq)

So the double salt is on a discrete level somehow acidic...it is known for ages that trace acidity inside nitric esters (like MHN) is bad news for stability and sensitivity.

2°)Silver nitrate acetylide complex when done without care produce a grey-brown or black compound in place of a creamy coloured solid...the darker the compound is the more sensitive it is towards friction...

a_bab - 31-8-2009 at 12:29

I had silver acetylide (carbide) goung off twice on me. I highly suspect a complex of it is prone to ddt even in wet state due to the crystal stress.
On the other hand, making a mixture of a HE with a primary is plain insane anyway.

User - 31-8-2009 at 15:39

Is it really that insane...

This way it is possible to use even smaller total amounts.
DS is relatively weak and one would need larger amounts to set off insensitive HE's.
By adding 50% MHN ( or other ) the power of the primairy charge is enhanched in a way that goes around just using more.

I cant back this up at the moment but compo blasting caps have been used commercially.

nitro-genes - 1-9-2009 at 07:49

Quote: Originally posted by PHILOU Zrealone

2°)Silver nitrate acetylide complex when done without care produce a grey-brown or black compound in place of a creamy coloured solid...

Except for AgNO3 and HNO3 concentrations, which conditions would further promote complex formation?

What would be the effect of impurities? Using calcium carbide gas generator instead of pure acetylene always results in slight discoloured product for me. No matter which synth I'm using. Tried using gas washing bottle with NaOH solution to remove H2S and PH3, still grey product... HNO3 and AgNO3 are PA grade, water used MilliQ... lol.

[Edited on 1-9-2009 by nitro-genes]

PHILOU Zrealone - 1-9-2009 at 11:26

Quote: Originally posted by nitro-genes

Quote: Originally posted by PHILOU Zrealone

2°)Silver nitrate acetylide complex when done without care produce a grey-brown or black compound in place of a creamy coloured solid...

[Edited on 1-9-2009 by nitro-genes]

-You can make 3 variety of silver acetylide:
1°) the neutral process, via bubbling C2H2 into silver acetate solution
2°) the basic process, via bubbling C2H2 into AgOH solution into ammonia water
3°) the acidic process, via bubbling C2H2 into AgN03 solution

The sequence of stability is 3>1>>2 and the sequence of power and VOD is 3>>1=2!

-To make the best stable silver acetylide nitrate complex and to get it as white/creamy as possible:
1°) Use demi water for the dissolution of AgNO3!
The use of tap water results in AgCl, Ag2CO3, AgOH, Ag2SO4, ... all insoluble induce darkening of the resulting precipitate by generation of black metalic silver.
2°) Use chemically pure AgNO3 if possible.
Unpure compound induce oxydoredox that favourise deposition of black metalic silver.
3°) Avoid by all means the refluxing of Ca(OH)2 aside with the C2H2 into the AgNO3 container. This causes immediate precipitation of AgOH source of black metalic silver (or black silver oxyde)
4°) Avoid as much as possible the contact with strong light (especially sunlight) during all the process (dissolution, bubbling, filtration, washing with H2O demi, air drying)
(Sun)light decomposes the AgNO3 and other silver salts into metalic Ag.
Under very strong sunlight exposition the complex might self-explode.
5°) If you use a paper coffee filter, wash it twice with demi water...this helps washing the chloride, sulfide, sulfate away from the paper...
6°) Note the rewash (twice) with demi water after the filtration, this allows to wash excess uncomplexed AgNO3.
The wash water can be reused in initial AgNO3 solution for further bubbling to get a second crop of precipitate.
7°)Air dry in the cold (25-35°C) and in the dark.
Then store in a PE film canisher.

If you follow those instructions, you get white to creamy precipitate that last for years without change and keeps all its abilities to the top.
Otherwise you get a grey to brown precipitate that get less and less stable as it turns darker.

[Edited on 1-9-2009 by PHILOU Zrealone]

hodges - 1-9-2009 at 14:13

Quote: Originally posted by PHILOU Zrealone

I have a small amount of silver acetylide, made using method #2, that has been stored under water for over 3 years. It started out white and has now darkened to dark gray. Just tested some recently and seems to act the same as before.

Hodges

PHILOU Zrealone - 5-9-2009 at 10:08

Quote: Originally posted by hodges

Quote: Originally posted by PHILOU Zrealone

I'm sorry it is my fault: by stability, I meant sensitivity (-> to shock/friction/heat). Stability of course refers as you stated to storage stability.

The number 2 contains some Ag3N, Ag2NH and AgNH2 nightmare of mirror makers...reason of its higher sensitivity than its neutral or acidic homologs.

nitro-genes - 6-9-2009 at 07:21

I've gone through most of the possible influential factors by process of elimination, including temperature of the AgNO3 solution, HNO3 concentration (Although not necessary below 10% AgNO3 solutions), speed by which acteylene was bubbled through, washing with different solvents to decrease drying time, influence of performing the reaction in the complete dark, etc etc.

At the end, I came to the conclusion that the most important factor that determines the quality of the complex must be the purity of the acetylene. Use of calcium carbide generators has been associated with dark coloured complexes, which is no suprise since calcium carbide involves a reasonably aspecific reaction at higher temperatures, producing numerous by products:

http://www.absoluteastronomy.com/topics/Acetylene -->

Impurities in acetylene are easily detectable by smell. Pure acetylene is a colorless and odorless gas. The characteristic garlic-like odor of technical grade acetylene is attributable to contamination by impurities. Impurities which may be present include: divinyl sulfide, ammonia, oxygen, nitrogen, phosphine, arsine, methane, carbon dioxide, carbon monoxide, hydrogen sulfide, vinylacetylene, divinyl acetylene, diacetylene, propadiene, hexadiene, butadienyl acetylene, and methyl acetylene.

The last 7 would be hard to exclude from the acetylene generated and could have impairing effects on the formation of the complex, perhaps by forming an unstable complex with Ag2C2 or AgNO3 themselves. Since with some batches of calcium carbide the complex turns brown/grey from the first bubble of acetylene, some impurities might reduce AgNO3 directly thus introducing metallic silver. Use of pressurized acetylene, which needs to be chemically pure due to safety regulations, could provide an answer...

[Edited on 6-9-2009 by nitro-genes]

watson.fawkes - 6-9-2009 at 08:04

Quote: Originally posted by nitro-genes

At the end, I came to the conclusion that the most important factor that determines the quality of the complex must be the purity of the acetylene.

Here's what Purification of Laboratory Chemicals has to say on the subject:

Quote:

Acetylene [74-86-21] M 26.0, m -80.8°, b -84°, pK -25. If very impure it should be purified by
successive passage through spiral wash bottles containing, in this order, satd aq NaHSO4, H20, 0.2M iodine in
aq KI (two bottles), sodium thiosulfate soln (two bottles), alkaline sodium hydrosulfite with sodium
anthraquinone-2-sulfonate as indicator (two bottles), and 10% aqueous KOH soln (two bottles). The gas was
then passed through a Dry-ice trap and two drying tubes, the first containing CaCl2, and the second, Dehydrite
[Mg(C104)2] [Conn, Kistiakowsky and Smith J Am Chem Soc 61 1868 1939]. Acetone vapour can be
removed from acetylene by passage through H2O, then concd H2S04, or by passage through two gas traps at
-65° and -80°, concd H2SO4 and a soda lime tower, a tower of 1-mesh Al2O3 then into H2SO4 [Org Synth Coll
Vol 1 229 1941,3 853 1955; 4 793 1963]. Sometimes it contains acetone and air. These can be removed by
a series of bulb-to-bulb distns, e.g. a train consisting of a conc H2SO4 trap and a cold EtOH trap (-73° ), or
passage through H2O and H2SO4, then over KOH and CaCl2. [See Brandsma Preparative Acetylenic Chemistry,
1st Edn Elsevier 1971, for pK p15, ISBN 0444409475; 2nd Edn Elsevier 1988, ISBN 0444429603, and Chapter
5 for sodium acetylide.] It is also available commercially as 10ppm in helium, and several concentrations in N2
for instrument calibration.

Note: OCR errors may remain.

hodges - 6-9-2009 at 15:57

Quote: Originally posted by PHILOU Zrealone

by stability, I meant sensitivity (-> to shock/friction/heat). Stability of course refers as you stated to storage stability.

The number 2 contains some Ag3N, Ag2NH and AgNH2 nightmare of mirror makers...reason of its higher sensitivity than its neutral or acidic homologs.

I played around with this some. I made some #3, and allowed a small amount to dry in several places on my cement patio. I also took some of the #2 I had left over from 3 years ago and allowed this to dry in several spots on the patio as well.

I found #2 to be more sensitive, but only slightly. Both #2 and #3 required a pretty good hit with a hammer to get them to detonate. For a friction test, I tried scratching the cement with a metal screwdriver. I had to press hard and scrape fast to get either to detonate. Perhaps the sensitivity for #2 decreases with age.

Hodges

edmo - 16-9-2009 at 03:59

All acids will eat through a lot more than you expect. I only trust LDPE and even not that far now.

I would not trust anything with a peroxide+.

1281371269 - 22-9-2009 at 11:38

LDPE isn't all that great - HDPE, PTFE, Acrylic also I think should be very chemically resistant. However HNO3 will turn even HDPE bottles brittle over a sustained period of storage.

I still have the acid marks on my desk from one particular accident of this nature...

prometheus1970 - 28-1-2011 at 12:41

If dissolving pure silver in HNO3 how many grams AG, how many ml HNO3? Then add a little distilled water before H2C2 addition or bubble gas through acid/AG soln.?

[Edited on 1-28-2011 by prometheus1970]

Dr.Bob - 2-2-2011 at 20:35

Reading up about accidents reminds me of a few "Doh" moments. Many are 20+ years old during my younger years as a chemist.

A friend tried to make TNT once in high school in a sink by mixing the toluene, H2SO4, and nitric acid in a polystyrene coffee cup while the teacher was out for a while. Not too good. The toluene ate through the cup within seconds. So he tried to wash it down the drain a little. The acid corroded the drain pipe, and then leaked on the supply pipe. A short while later, the pipe suddenly burst, shooting hot water all over, especially on my friend and his stuff who was sitting next to it. Fortunately, the teacher did not find out what he was up to. The maintenance guy was complaining about how corroded the pipes had gotten.

Another guy I knew in college made a reactive mixture, played with it some and then went off to college after a while. He left the excess material in a glass jar under his bed... His family called after the house caught fire, and the fire Chief was asking about the "accellerant" in the bedroom. I think he claimed that he had some fuel for a RC car or plane and eventually was not charged. But his bedroom was burned badly.

I tried to make acetylene as a kid and succeeded, only to find that when I burned it, it created thick black smoke that stuck to the white curtains in the bathroom. <y mother was VERY unhappy, and all new experiments went outside...

Fortunately, as next I was playing with sodium peroxide (it used to be easy to purchase really hazardous chemicals 30 years ago...) and my reactor, a paper cup, burst into flames spontaneously on a humid summer day. After that I found that you could pour a bit on a paper towel, roll it up, spit on one end and start a fire easily, even with wet wood. Even better with wet wood... I had some boy scout friends really amazed.

Tried to make some rocket motors with Zn and sulfur. Worked a few times, biggest one just blew up in an enormous cloud of smoke. Neighbor thought that their house was on fire.

Best one was making a "model" volcano for school project. It was 2' by 2', with a 16 oz tin can as the top opening. I had filled it with 1/4 layers of thermite, flask powder, smoke mix, Ammonium dichromate, etc to the top. The teacher must have assumed I was going to mix NaHCO3 and vinegar, but I suggested that it would be better to demonstrate outside. It shot flames 3 feet high and created a smoke cloud a block wide. Some teachers saw it and thought the school was on fire. But the kids in my class were amazed, and I think I got an "A". But the teacher suggested that I keep my chemicals at home. Now I would be a terrorist.

Another time, I asked the teacher what would happen if we mixed KMnO4 and glyerol. She didn't know, she we tried. Yet another large flaming beaker, fortunately small scale and on a soaprock bench. Thankfully, also not under a sprinkler head.

Perhaps you see a trend here. Some of my friends somehow got the impression that I was a pyromanic or something. Looking back, I wonder how I didn't catch my house on fire, burn myself or get arrested. But now I am a productive member of society (who happens to still like fire, but is more careful).

Bob

prometheus1970 - 3-2-2011 at 07:12

I appreciate the anecdotes (I have several of my own). I've learned to be more respectful of primaries. Once again, though, It was not carelessness that caused my mishap, it was poor judgement. I apologize if you already understand this, but everyone seems to think I was just smoking around a pile of explosives like a dumbshit when it went off. However, that was not the case. I was testing a tiny piece of Ag2C2 for dryness/ viability by holding a lit cigarette to it without properly shielding the remainder of the batch from possible flashover. I do appreciate your reminding me of the potential dire consequences of this hobby. I just want to be sure everyone understands it was not a case of blatant carelessness, but one of a lack of foresight.

avi66 - 3-2-2011 at 08:24

Don't use a PET plastic bottles to hold 70% nitric acid!!!
i just used one to hold 1 liter of this stuff, and its eat the plastic and eat all my wood lab closet ! make all my wood yellow, and almost react with the sodium hydroxide inside my wood closet !

prometheus1970 - 3-2-2011 at 10:21

I don't use plastic bottles to hold HNO3. I mentioned using an LDPE bottle in my Ag2C2.AgNO3 synthesis, but that was just the gas generator part.

p.s. what is "PET"?

[Edited on 2-3-2011 by prometheus1970]

gnitseretni - 3-2-2011 at 10:33

PET is plastic with the number 1 in the triangle. Use #2, 4 and 5 (HDPE, LDPE and PP) for HNO3. I've used these without a problem.

ScienceSquirrel - 3-2-2011 at 10:41

Polyethylene terephthalate, being an ester it is not surprising that it reacts with nitric acid.

http://en.wikipedia.org/wiki/Polyethylene_terephthalate

peach - 4-2-2011 at 19:12

PET is not a good choice for storing strong acids. I would be cautious storing anything but relatively inert stuff in it.

HDPE is about the best resistance gets in terms of plastics before you switch to fluoropolymers. It is usually more resistant than PP as well. Every bottle or container of chemical I've ever got in plastic has been in HDPE. HDPE is transparent, but things are added to it to make it white and more solid looking. With regards to resistance and extractables (which contaminate the contents), the transparent stuff is likely better.

Ultra high molecular weight polyethylene is used in bullet proof shields. Another useful property of UHMW-PE is that it's co-efficient of friction is not far off PTFE's, but PE is thermoformable whereas PTFE is not. PE is also used for permanent plastic traffic bollards. And, everyone's favourite, shopping bags.

I have painted the surface I do chemistry experiments on with polyurethane floor paint. It's not perfect, but it is more resistant than most other finishes and can be scrubbed clean again. I spilt concentrated sulphuric all over it just recently, when the rubber seal on a valve I was testing fell apart. I've had extremely concentrated base solutions on there as well, and solvents. The surface is certainly marked, the worst being from iodine, but it's not peeling off or blistering.

A dish would be a good idea, but I'm not too bothered about the surface getting mucky. If you're doing chemistry inside, over carpets, some method of containing things is far more important, when a carpet alone can cost hundreds of pounds.

In terms of faulty electrical equipment, my hotplate's controls stopped functioning properly quite early on it's life. I had suspected something fishy was afoot for a long, long time, as the stir bar control would seem to not cause any change in some regions. One day I remembered that my pH meter, which also has a temperature probe, came with a CD and that I could use it for data logging. I installed it on a really old, unused laptop and decided to put that on the surface with my chemistry experiments, so I can read the forum and references as I watch something going beside me.

I was heating a flask of water on the plate and stuck the thermometer in, then decided to see how linear the temperature control on the front was. Plotting the graph and seeing it appear in front of me, I was quite surprised to find not only regions where the temperature wasn't rising as I increased the setting, but FALLING.

The only thing I can attribute this to is reactive gas getting behind the controls, into the pots and onto the tracks inside.

It's not a major issue though. I can try giving them a clean or simply replace them. Pots are not expensive and just need a few minutes with a soldering iron.

Sedit - 4-2-2011 at 19:41

I had a small accident the other day that could have been worse then it really was...

I was testing my new homemade mini kiln when I wanted to see how it performed in a reduction firing. Last minute on cool down in this type you supply some sort of fuel being carbonous material like newspaper or something like Methanol. I chose methanol for its smoothness. So there I am dripping drop by drop as each flares up as it enters the kiln, nothing exciting hence the issue. For about 30 minutes I did this and after a while I just started to drip it from overhead streight from the bottle which went well for a while until I got overzelous with a big splash and it ignited the bottle of Heet in hand.

LMAO, it shot the remaining Methanol out of the bottle with such force it didn't have time to ignite it, thank god, and recoiled the bottle out of my hand backwards. Nice little woosh sound and I lost more then likely 5 years off my life but in the end no harm no foul(ok a little foul but alls well).

peach - 4-2-2011 at 20:50

When do we get to see photos of the kiln?

I'm getting all excited by the constant teasing.

Sedit - 4-2-2011 at 22:50

Soon enough, Not much to look at honestly, just what looks like a little mud beehive from the outside but effective non the lest, Im just praying that the element holds up long enough since I really didn't implement a means of changing it

. I started small but after a couple little test runs ended up adding about 2" more of insulation and as of right now the lid has not been fully reinsulated but progress is there no doubt. I ran a test tonight to gage the temperature that it rose and it took about 45minutes to reach 1000 degrees F and about 2.5 hours to reach a little over 1500 degrees F.

peach - 5-2-2011 at 12:16

If you go for a Mk2, it might be worth looking into breeze blocks; metal researcher has tried them quite a few times and found they're a good source of cheap insulation.

There is also aerated concrete block, which has a low enough density it can be cut with a wood saw.

I have all those high temperature refractory bricks, not they're not very good insulators. I might have a go with the aerated blocks as an outer liner myself.

White Yeti - 31-7-2011 at 09:24

That's one hell of an accident! Making mistakes happens to the best of us, unfortunately.

The interesting thing is that right before something bad happens, you got this gut feeling, "something's not right", "maybe I should put the acid in a glass beaker just in case", "I should keep an eye on this, just in case". I have never met an experimenter who has not had a gut feeling right before something actually went wrong in the lab.

Fusionfire - 31-7-2011 at 13:13

Quote: Originally posted by Polverone

Until yesterday I didn't think that any common acid (including sulfuric) would attack plastics either. I don't know what sort of plastic it was; the bottom of the bottle holds the recycling code that tells what type it is, and it was destroyed. The bottle was originally used to hold sterile eye drops for use with contact lenses. I thought it would make a nice dropper bottle for small amounts of H2SO4 indoors (since I store the big jug outside in a cabinet). I came into my room and thought things smelled a little funny, but I was doing a reaction on the hotplate so I didn't think too much of it. Then I saw over on my shelf that there was a puddle of acid formed, and a thin stream falling on the table below the shelf. The acid was coming from the bottom of the bottle that I had set there.

When I tried to pick up the bottle to put it in a glass pan to take outside, the whole bottom fell away (that's when the acid went down the wall and onto the carpet). If I'd been thinking a little better I would have set the glass pan up to catch the acid instead of trying to move the bottle. But, of course, many things could have gone better (or worse) yesterday.

I am not too worried about vapors from this incident damaging computer equipment. I do think that my monitor is suffering progressive failure from exposure to various fumes, though. I was aware of the potential problems but this monitor has lasted several years and has a big scratch on the screen (from careless handling by someone moving it) anyhow.

There were probably 300-400 mL of acid in the bottle at the time of the incident.

You can get a rough idea of the type of plastic by feeling how hard it is. Hard plastics are usually thermosets (e.g. epoxy, bakelite) while softer ones are usually thermoplastics (e.g. polyethylene, polypropylene).

Thermosets are more susceptible to chemical attack because of their many functional groups; more functional groups implies more incompatibilities.

Thermoplastics with linear carbon chains and attached H or F atoms (e.g. PP, PE, PTFE) are obviously the least complex and least susceptible to chemical attack of different plastics.

[Edited on 31-7-2011 by Fusionfire]

perry798 - 24-9-2011 at 13:53

Be VERY, VERY careful indeed when working with hydrogen selenide!!! I found out why - THE HARD WAY!!! By accident I exposed myself to a HIGH concentration of the gas. The first sign of danger was the change of odor from rotten radishes / 'gas' to STRONG ODOR OF ROTTEN EGGS. I stupidly ignored this warning. Suddenly without any further warning: my nose started STINGING / BURNING UNCONTROLLABLY - NO MATTER HOW QUICKLY I RUSHED TO THE NEAREST WINDOW. Still the UNBEARABLE STINGING / BURNING WOULD NOT GO AWAY, OR EVEN LESSON IN THE SLIGHTEST!!! SEVERAL hours later the stinging / burning in my nose was tolerable and had almost gone - only to be left with a nasty cold that took at least a few days to get over. I could have only been exposed to the gas for a few minutes at the most - while I was transferring some aluminum selenide from one container to another. By the way - always store and handle aluminium selenide away from even air!!

White Yeti - 25-9-2011 at 04:15

Quote: Originally posted by perry798

Be VERY, VERY careful indeed when working with hydrogen selenide!!! I found out why - THE HARD WAY!!! By accident I exposed myself to a HIGH concentration of the gas. The first sign of danger was the change of odor from rotten radishes / 'gas' to STRONG ODOR OF ROTTEN EGGS. I stupidly ignored this warning. Suddenly without any further warning: my nose started STINGING / BURNING UNCONTROLLABLY - NO MATTER HOW QUICKLY I RUSHED TO THE NEAREST WINDOW. Still the UNBEARABLE STINGING / BURNING WOULD NOT GO AWAY, OR EVEN LESSON IN THE SLIGHTEST!!! SEVERAL hours later the stinging / burning in my nose was tolerable and had almost gone - only to be left with a nasty cold that took at least a few days to get over. I could have only been exposed to the gas for a few minutes at the most - while I was transferring some aluminum selenide from one container to another. By the way - always store and handle aluminium selenide away from even air!!

I know what you mean. I have a container full of aluminium sulfide. And not only is it sealed, stored with obnoxious amounts of desiccator, but its also wrapped in tape, covered with bubble wrap, contained in two ziplock bags and stored on the lowest shelf behind all the other containers. I'll find the courage to use it someday....