My Chemical Mishaps
Introduction:
Why did I have so many mistakes? Likely it extends from my lack of formal education at the time. Still, that can't be blamed in its entirety since no where in my college career did they explain the proper way to run a molten salt cell or deal with high temperature liquid phase oxidations. Sure, you can learn a lot from a book, but it's not a perfect substitute for actually learning hands on. Over the years of doing chemistry at home I had more than my share of screw-ups. Many of them in retrospect are pretty funny or informative. So I decided to make this page to go with the other content of this website for a more complete picture of things. Read all you want, don't try this at home, and enjoy. The goal was to put these in chronological order but some of them may be a bit out of step, however little impact that has on anything.
Neutralization of Sulfuric Acid
One of my very first organic experiments involved my attempt to make diethyl ether. At the time I wasn't quite 14 years old but I had a lot of ambition. No, I didn't have any malicious purpose in mind, and it wasn't just a means to an end, it was the end. I just wanted to make some ether because my middle school chemistry book told me how and the reagents were accessible to me. So, I took a 3000 mL Erlenmeyer flask and charged it with 250 mL 96% H2SO4 and added about 50 mL ethanol. I put a big ol' rubber stopper in the Erlenmeyer it and cut a hole in it with a knife. From there I ran some tubing from it and into a 72 oz soda cup from the convince store where it spiraled down through some ice and out the bottom to collect in a beaker. Then I heated it on a electric camping stove (one of those portable oven coils) and waited.
It started bubbling and eventually I got some milky distillate (I figured the color came from the tubing. It ate the heck out of all the plastic and rubber, but what the hey, since when did I notice the obvious back then, most of it probably turned to ethylene anyway). I continued cranking on it and the stopper melted and started running down the inside walls of the Erlenmeyer, 'Time to turn it off' I thought. So I pulled the plug and yanked out the stopper which was hanging by the tubing over the acid and still melting. The mixture had stopped evolving gas so I assumed all the ethanol had been driven off. Wanting to dispose of it right away (and being environmentally conscious) I figured it would be best to neutralize it before tossing the mixture.
Thinking quickly I grabbed the only base that I had at my disposal, some sodium bicarbonate. It was still in the little orange box it came in from the grocery store. I grabbed the whole box and tipped it over the sulfuric acid. The sulfuric acid that was quite concentrated, the sulfuric acid still at about 200°C, the sulfuric acid that was about the blow up in my face as a huge chunk of the bicarbonate fell unbroken into the acid. The eruption from the flask was huge and I immediately threw myself back and landed on the ground, trying to get some distance. Miraculously the flask held in one piece, channeling the sulfuric acid into a torrential shower of acid rain. It came down, sizzling as it hit the ground but I was already scurrying toward the door of my house. Not knowing if I got anything in my eyes or on my face I immediately went to the sink and washed for about five minutes, then inspected myself. I got some on the arm of my shirt but nothing major. However, the picnic table did not fair so well, it was now severely charred in areas and the hot plate I had used to heat the mixture was quite the wreck too. A nice start for that picnic table which served me through nearly a decade more of my chemical mishaps.
Lesson Learned: Do not neutralize hot concentrated acid, especially with any carbonate or bicarbonate!
Acetone Peroxide
The set up for this one is quite laughable. But this one takes place a bit later in life. It is now the ninth grade, my first year of high school, and with that comes a new chemistry book! So, of course I read most of it before the class even started, looking at all the cool pictures and everything. One thing however caught my eye. My young mind was working overtime, "Hmmmm.... I didn't know you could make chloroform from chlorine gas and methane.... methane comes out of the gas lines at home, I can make chlorine gas, I can make chloroform, I'd be so cool!" So I devised a project, which is somewhat occluded in my mind now, involving a trash bag full of methane and chlorine that I would put into a large container of boiling water to prepare chloroform (I always thought the chloroform would be green, probably because chlorophyll is). Anyways, I decided to run it by my teacher, of course he freaked out. He said there was no way I could make it in my backyard like that or that I should be doing much of anything at my age. So I asked if there was any way I could. He thought for a minute and said something about there being a reaction (at the time he might have mentioned the haloform reaction or my brain might have just been trying to fill in the gaps later in life) He phoned my mother and told her what to do to demonstrate it to me. I got home and a couple days later I saw my first haloform reaction. Basically he told her to mix bleach and nail polish remover.
Of course he didn't want me dealing with the stuff, that's why he didn't tell me how to make it, but all I had to do was ask my mom what she mixed and she told me right off and thus I could prepare chloroform. But I never got much of it. Eventually I ran out of reactants and started buying them in bulk. (Mind you, it used to be whenever I would find out how to make something, and would actually be able to do it, I would stockpile it like it was going out of style). Yields where lousy with bleach and acetone so I figured it was because the sodium hypochlorite was too dilute. I tried to substitute what I was using for a chlorine source and after failing with straight Cl2 (chloroaceone, that's another story in itself... my eyes hurt just thinking about it) I decided on trying hydrochloric acid as my chlorine source. I mixed my acetone with HCl and no reaction could be seen. So I started trying to figure out how I could get the HCl to fork over some of its chlorine and after looking at the structure for sodium hypochlorite I decided to add some oxygen to the mix. I tried mixing some concentrated hydrogen peroxide with HCl and got some chlorine gas, e.g. it started to smell more like bleach, so, success!
Upon finding this out I took equal volumes of HCl, Acetone, and 10% H2O2 adding up to about 400 mL and mixed them. (I knew nothing of the small scale, my smallest beaker was 250 ml and I hardly used that one). You know what happened next, a nice white precipitate, some boiling, some terrible burning of my eyes and a couple hours later, a pile of white crystals. Mind you I had no clue what I had made so I took it and added some sodium bicarbonate to it and see if it dissolves since it is acidic to luminous paper (it was soaking in 20%HCl, what did I expect?). Eventually the product came out neutral and it was not dissolving in water like I thought it would. I figured I made something new.
Testes were simple, I thought that I had completely chlorinated acetone to CCl3CCl2CCl3 because it reminded me of hexachloroethane. I was wrong but it was only after a couple weeks when I got back to testing it that I figured it was something different. I tried dissolving it in all the solvents I had, nothing really quantitative. I only had about 1 year of crappy chemistry at this point. Eventually I wanted to see if it burned and I got a giant fireball. Now, to me this was like Christmas come early. I've never been into chemistry for the bang or the boom but I think everyone of us has a soft spot for fire somewhere. First thing I did was start mass producing this stuff thinking that it was like flash powder. I would constantly light quantities of it with a blow torch and never had a problem. I stored it in plastic screw top bottles and treated it like any other chemical. Fast foreword by about a year. I found out this stuff was explosive when I wanted to see what it would do if confined, five grams between two sheets of duct tape, it was quite the bang. So now, with the newly acquired research tool of the internet I decided to do some sleuthing. Still this was several years ago and the internet was a different place, most of the references that I found online for the home chemist at the time had chemistry and pornography on the same page.
Regardless, after searching for a couple days under many things I eventually found it by looking up some strange combination of key words. The page I found, which has since been taken down was a story in a news paper about some kid in the South-West USA who had made a small quantity of this stuff, 10 g and had blown his hand off. So of course I was freaking slightly with about 500+ g of it in the shed. It went on with an expert who explained that acetone peroxide is highly sensitive to friction and such. So, as I read more and more and felt the pit of my stomach sink I had to formulate a game plan to get rid of this stuff, and quick..... and now it's gone.
Lesson Learned: Do not make large quantities of a compound you don't even know the name/structure of!
H2SO4 / HNO3
1) Most people I've talked to have either succeeded, or at the very least attempted to distill HNO3 from a mixture of H2SO4 and KNO3, well I've got two tales of woe that accompany this school of thought. For my first attempt, I took a volumetric flask and filled about 1/8 full of KNO3 and sulfuric acid 90% ish. I put the flask on its side on a heating coil and put the neck into a flask cooled in an ice bath and commenced heating. I watched and became overjoyed when I actually started getting distillate, but it was getting late and dark outside. My care giver that I was living with was yelling out that it was getting really late and I had to put up my stuff now. So I started picking up a bit, everything non-essential. Finally just the flask, the ice bath, the volumetric, and the heater were left out. So when it suddenly started raining I decided to start putting this stuff away. I pulled the plug on the heat and put what distillate I had into a separate container. Then I picked the flask up with my glove, which started to melt considering it was at 130°C give or take 30°C. Looking for a quick cool down solution I did something that seemed stupid even at the time, I picked the flask up off the heating coil and put it into the ice bath, I started sizzling but held together which made me think that it was okay, then I put it in some more. The whole thing exploded in my hand sending scalding sulfuric acid/nitric acid/potassium nitrate all over me. I ran through the house straight into the bathroom and turned on the shower, removing my clothes as I was getting drenched, one particular spot of clothing over my stomach was being eaten away right while it was on me. But about 40 minutes later I emerged with some 'minor' acid burns over my arms and one on the right side of my face.
Lesson Learned: Borosilicate glass is not immune to thermal shock, don't be stupid!
2) Flash foreword a good 2 years to where I have my first good all glass 24/40 distillation setup. Same experiment with a higher concentration of acid. The distillate was carrying over good and all but it was a bit dark. I assumed that it was just red fuming nitric acid. Forty five milliliters of distillate and almost all of it was NO2, I was using it like it was water, kind of funny really, I almost died considering the toxicity of it.
Lesson Learned: Just because I think I know what the product is, that doesn't me that's what it will be.
What's in a match head?
1) When I first started to look up the composition of a match head, most of my references were nearly 40 years out of date, so I discredited them all as unreliable and decided it was time to do a full investigation from scratch. After all they used to use white phosphorus in match heads and no one does that anymore, right? Having a rough outline of what was in them I went on my quest. Step one: Buy tons of matches and cut off their heads Step two: Dissolve the heads Step three: Figure out what's in them. Step two is what got me, match heads are kind of hard to dissolve, especially if you are impatient, so into my workshop I went and used every liquid I had to illicit a response. I ended up using 20% HCl which made quick work of small amounts. Plan in mind it was time to scale it up. So, I took about 500 match heads and tossed them into about 300 mL HCl. I had done this on smaller scale with no problems but shortly after starting it on the larger scale I knew something was wrong. All the match heads were submerged but the mixture was sparking, then there were small explosions... Then- it detonated. Now I know that it was the chlorate in the heads generating chlorine dioxide by reaction with the HCl, but back then I was just like "OH MY FREAKING GODDDDD!!!!!" Thankfully the beaker was in the center of my yard with a piece of paper over it, certainly the paper reduced the ballistic velocity of the glass but not enough to stop it from sinking into the fence.
Lesson Learned: Even if something works on the small scale it doesn't mean it will work or be safe on the large scale.
2) Second attempt at the same thing, I figured that I could take match heads, mix them with water and heat them up, hot boiling water would strip the heads and I could study the composition. So again I took about 500 match heads and tossed them into 500 mL cold water then slowly heated in a coated pan. Just like I thought, the mixture turned red then the cardboard backing for the heads started bobbing around on the surface. So I strained it, then the phosphorus sulfides broke down and I got several grams of sulfur that started floating around, finally after sulfur stopped popping up I put it into a piece of cloth and really strained it, inside of the cloth was about 40 g of ground glass, potassium chlorate, and potassium perchlorate with some other fillers. I put this to the side and continued to heat the remaining liquid. Eventually it got to a paste, and the person that was helping me out said "It looks like it's about time we took that off the heat" but I wanted it on for a few minutes to ensure it was completely dry. I was stirring it and then there was a dry spot, when I saw it I knew that it was done, but just as I was moving it off it burst into flames, a large gout of flame shot 10 feet or more into the air and as it was doing this I managed to kick over the pan which pushed itself across the yard a bit before burning out. All the while my friend was screaming at the top of his lungs. The pan was badly warped and was thrown away.
Lesson Learned: Do not evaporate to dryness unless you have to, especially pyrotechnic compositions!
Silver Thermite
Well, it all started when I had some silver wastes lying around contaminated with copper. So, I had to figure a way to separate and purify. I took the silver/copper nitrate solution and added to it some sodium hydroxide. That precipitated the silver oxide and the copper hydroxide. I dried this a bit then added to some HCl, this dissolved the copper hydroxide and left (most of) the silver oxide. Then not wanting to loose any of this in the thermite reduction I had planned I decided to bind the silver oxide with the aluminum powder using sulfur, seeing as how it would just turn into gaseous sulfur dioxide when used as a binder compared to my other option plaster of Paris which would require more refining. So I took my silver oxide, my aluminum powder, and my sulfur and mixed in a pan under increasing heat. Eventually I could not tell there was even any sulfur added, I expected it to at least get goopy or something so I added some more and more but it continued to stay free flowing and powdery. Finally even though I really couldn't tell a difference I figured enough was enough. I was loading it into a short length of copper pipe as a mold with a spoon when the whole mixture went up. It could have been from the residual hydroxide on the silver oxide reacting with the aluminum under high temperature, it could have been that enough heat had been formed to initiate a reaction since I was no longer stirring it, it could have been a lot of things but I swear I could smell hydrogen sulfide in there somewhere... I was wearing cut resistant Kevlar gloves but that wasn't enough, and my face shield turned into a twisted flaming piece of debris, the mixture deflagrated and went everywhere splashing silver over everything. The ground was all on fire and I was trying to calm myself as I looked at the glowing red liquid solidifying in the pan. I took stock of the situation, gloves intact, most of my hair still here, no obvious burn holes, no hair on my left arm, not too bad... Then I took the glove off my left hand, and most of my skin came with it. I had to spend 5 months in a glove to protect my new skin from the sun while waiting for it to heal, but I did get to lecture the doctor at the hospital about his lack of chemistry skills.
Lesson Learned: You can never take for granted the properties of a pyrotechnic composition, always wear proper protective gear.
Phosphorus!
For my first honest to goodness attempt at phosphorus I used a metal container roughly the size of a propane can for a camping stove to perform the reaction in. From it I lead a metal pipe 3/4 inch wide that bent under the water to condense the phosphorus. Initial heating was accompanied by minimal gas evolution. Then suddenly massive gas eruption, constant bubbling and to my surprise and fear the bubbles were busting into flames instantly upon going out of the water. The pipe leading into the water was corroding before my eyes. Literally there was rust coming off it rapidly. I turned off the torch and watched from upwind as it continued to bubble. The smell was unmistakable, I had crossed over into phosphine territory, for those unfamiliar with the chemical it is exceedingly toxic. It is somewhat similar to phosphorus in the body, there can be a latent period of days after exposure with no side effects then BAM you’re in the ground dead with a hole in your liver the size of a baseball or your lungs full of fluid, even worse. The LD 50 is pretty low and poisoning is pretty common from this crap, and it catches on fire way to easy for my liking.
A gas mask was in order so I took a break. When I came back I noticed there was a considerable amount of phosphorus but the phosphorus was condensing as a 'cork' phosphorus which floated on the water and I watched in amazement and sadness as the phosphorus caught fire on the water and went away. I cranked the heat back up full blast, but was rewarded with nothing, the slag from the reaction I had initiated had solidified on the bottom of my reaction vessel and was preventing further reaction. So I turned up the heat more and more.
Still nothing, finally there was fire everywhere, the bottom burned out and there was quite a bit of phosphorus and slag in there, the puddle was spreading quick and blazing. Phosphorus pentoxide was on the wind and the smoke screen was pretty intense, once again upwind with me. Knowing that the reaction was a no-go any further I grabbed the reaction vessel and set it in the dirt to cover the bottom and the nozzle where the phosphorus was coming out. I started to clean up a bit while it cooled off. Eventually I got back to the vessel and picked it up, the ground underneath it was covered in hot phosphorus which immediately took fire and as I would have never predicted the whole vessel was filled with phosphine which promptly exploded, throwing the vessel out of my hand, putting me on the ground, and spreading phosphorus everywhere as a consequence.
It was all on fire, water was no good it just caught again. I was getting angry and that stupid can kept filling with phosphine and blowing up, over and over again. Now it was time for a really really stupid thing on my part.... I poured WATER into the can. Mind you, the thing furthest from my mind is that the phosphine might in part be coming from ambient moisture in the air reacting with the abundance of aluminum phosphide currently residing in the container. When the water hit it, it really started booming, it shot water and debris into my face and escaped from under my foot. The phosphine coming out was also impregnated with small particles of phosphorus and its vapor immediately gave rise to spontaneously flammable conditions, it would explode, fly into the air, and while in midair fill with phosphine and blow up again.
I had to think fast, I grabbed a shovel and started digging. I had to take off my welding gloves because they kept catching on fire from the phosphorus on them and my pants were charred in areas. As I walked around I was leaving smoking footprints from the phosphorus on my feet from trying to stomp it out. Everywhere phosphorus was being flung and the air was full of smoke and the ground was on fire, "Welcome to hell" I said to myself. The hole I dug was bout 4 feet deep. I had taken off the majority of the pipes on the apparatus by holding the chamber beneath my foot and twisting them till they gave. During its down time I grabbed it with a pair of gardening shears and tossed it in the hole. I buried it and placed rocks on top of it. The ground all around it smoked and looked like it was smoldering. It took 3 days for it to stop doing that. Once again all my phosphorus was corky so my yield was really terrible.
Finally, the lasting legacy, the clean up. I let the phosphorus in the yard burn out and put the pipes in my back yard. They smoldered from a good five days and when I took them apart they bust into flames. When I cleaned them they burst into flames, when I looked at them weird they bust into flames, heck, let's face it, they were busting into flames just to be bursting into flames. I tried a bunch of solvents, one that struck me as odd was olive oil, it was listed in my chemical encylopedia but it works like crap and it smells horrible afterwards and that itself is hard to get off. Finally though I got them clean enough (need better solvent for phosphorus....) and the nightmare was over.
Lesson Learned: Be careful what you wish for... (and get a good strong reaction vessel!)
Working with Molten Hydroxide
The weather was supposed to be clear and the day had come to setup my Castner cell. It held an incredible 4 kg of sodium hydroxide and the electrodes had been expertly placed into the mixture beforehand. Melting everything was quite the chore but once it was molten it stayed molten. Electrolysis of the molten sodium hydroxide continued for some time and I wondered to myself "I wonder how things are going?" Because the anode was blocked from view the curiosity eventually got the best of me and I moved the wood plate off the top. Little did I know the bell that was supposed to keep the sodium within had gone too low and shorted out the cell, causing the sodium to pool outside the bell. When it hit the air it burst into flames. Hummm... not a good thing. Minor explosions ensued but I stepped back and watched, even snapped a few pictures.
Electrolysis continued as normal afterwards, I lifted the bell up so it wouldn't short out any more and let things go for quite some time. But.... what's that on the horizon, it couldn't be rain, there was a 0% chance of rain today, it couldn't be rain, and so I kept telling myself until... it started to rain. Now, the sodium hydroxide was at 330°C give or take and it reacts exothermically with water at normal temperatures, not to mention there was substantial sodium metal probably dissolved in the melt. The first drop of rain hit like a hammer, spattering molten hydroxide everywhere, the table, the pan, my arm.... "OOOooohhhahhhahha It burns!" I jumped around from foot to foot and ran inside to get something to cover the cell. I got an umbrella and put it in a chemistry grippy claw to hold it above the melt. But I got nervous about doing this sort of experiment with rain dripping everywhere. The cell itself was in danger but I had something else to put the hydroxide in, I had a pan with a lid. I set it down on my picnic table, and picked up the pan with the hydroxide in it. It was incredibly hot, I had to take off one of my welding gloves and wrap it around the handle then grab the handle with the hand that had a glove, the glove underneath it started to smoke. Nevertheless I eventually finagled the pan out of the cradle I created for it and poured some in the pan. In the meantime I didn't think that water would be falling into the pan.... very bad. I poured maybe 50 mL of liquid NaOH in the pan and [Whooosh!] Hydroxide went everywhere again! On me, the table and on me. I struggled through the pain and put the pan in place, it had the cathode sticking out the bottom so the only place it could really go was back in the cradle. I managed to get it in and improvised a lid. I let things cool naturally as I went inside to wipe down my arm with vinegar, NaOH leaves nasty swollen wounds. And thus ended my second Castner cell.
Lesson Learned... have I already learned to have a contingency plan yet? Oh, and don't trust weather forecasters, and beware of extensive reactivates.
2) Another day, another Castner cell. This one was a few designs down the road from the one listed above. The previous cell had a distance between the electrodes of 1.5 cm but they were too close and shorted out. The only difference between this one and the pervious one was that the distance between the electrodes was increased by 1 cm and I had a heating coil wrapped around it. Heating was begun and molten NaOH was added and electrolysis begun. It worked well, everything stayed molten, more NaOH was added, bubbling was going on. I was happy. Until I had enough NaOH and stopped adding it but the volume kept rising. I cut the power but it was still boiling, "This is nowhere near the boiling point, what the hell is going on?" I looked underneath the cell, some drops were collecting, the NaOH was reacting with the material that I had used to plug the bottom. In previous runs I got some pitting but now, with the increased area that was needed to plug between the increased electrode distance, a reaction was occurring. It was getting close to eating through, I had to act fast unless I wanted a massive release of molten hydroxide which I had no doubt would set my table on fire and splash about. I ran and grabbed a 5 gal bucket and filled it with water. Meanwhile the bubbling of the solution had not slowed. After filled I grabbed the cell, stood back a few feet and tossed for the bucket. Immediately after it left my hand I ran. And immediately upon hitting the water, steam, NaOH, and water geysered out of the bucket with tremendous force. 5 gallons of water instantly raised to the boiling point. It was a most spectacular failure.
Lesson Learned: The physical and chemical properties of a substance can change greatly based upon the exposed surface area.
3) It is now a year or three down the road from when I did my experiments involving a Castner Cells and my eyesight was noticeably impacted by it. I didn't always wear goggles around it but even when I did my eyes would tingle and burn. Bases are notoriously bad for the eyes so I should have been more careful. Although molten NaOH has a higher vapor pressure than solid NaOH I think the actual culprit was the hydrogen and oxygen bubbles during electrolysis creating micro fine sprays of NaOH.
Lesson Learned: Always, always wear goggles, not only can things go wrong but there could be extraneous consequences down the road.
Yay! It was time to test out my photochlorination apparatus on tetrachloroethylene to make an attempt at carbon tetrachloride. Simple enough, right? So, my method of choice to make my chlorine gas..... adding concentrated sulfuric acid to calcium hypochlorite of course! So, I set up my apparatus, with a chlorine generator that consisted of a two neck flask with one neck containing a regular 250 mL separatory funnel and the other neck containing the exit tube for the chlorine gas. I powered up the UV chamber and got everything ready and added some sulfuric acid to my hypochlorite with a simple turn of the stopcock. The air within the flask yellowed a bit and I added some more, little bubbles started to come up through my sulfuric acid drying bottle and started going into the soon to be chlorinated tetrachloroethylene. A few bubbles were coming out of the exit gas section and were passed through some concentrated sodium hydroxide, but not at the rate at which they were passing into the chlorination chamber so I was hoping some was being uptaken. It was a little over five hours later when the powdery substance in the gas generation chamber had solidified in areas and become a paste in others, the stir bar was no longer helping matters.
I added some more sulfuric acid and nothing happened. I added more and after some prodding a small amount of Cl2 was expelled. I figured most of the hypochlorite in the flask had been exhausted. So, I opened the stopcock and let the sulfuric flow. The funnel was not pressure equalized so some would drip in, then stop, and more would drip in, then stop. So I went off to do other things, like inspect the UV chamber. But as I was looking away I heard a popping sound. The top of the sepretory funnel had popped off and sulfuric acid along with a cloud of chlorine gas had taken to the air. I thankfully missed the bulk of the sulfuric acid but the chlorine... I got a massive lung full, several in fact. I grabbed my gas mask and through a fit of severe coughing closed the stopcock and stopped the immobile stirbar. The pain as incredible and the coughing non-stop. It was nearly an hour before I was able to take a breath that was anywhere near normal.
Lesson Learned : Actually, one I learned before, make sure you fasten the stopcock in place in a gas generation apparatus. Additionally, be wary of compositions that do not give a consistent supply of gas, should have made it into a slurry first.