nitrogen trichloride & nitroglycerine
- sweat of the devil -
nitrogen trichloride & nitroglycerine
In 1811 Pierre Dulong (1785-1838) was experimenting with chlorine gas and a solution of ammonium chloride. An oil - nitrogen trichloride - formed. It violently exploded, costing Dulong an eye and three fingers. Dulong continued working with NCl3 after this horrific accident
Ampère wrote to Humphrey Davy concerning the discovery and Dulong`s accident. Davy repeated the experiment, produced a quantity of nitrogen trichloride "scarcely as large as a grain of mustard seed" and had this to say, after removing glass shards from his cornea, "The fulminating oil which you mentioned roused my curiosity and nearly deprived me of an eye. After some months of confinement I am again well."
Faraday, Davy`s assistant at the time, helped with a further four detonations until, he writes, "The experiment was repeated again with a larger portion of the substance. It stood for a moment or two and then exploded with a fearful noise; both Sir H. and I had masks on, but I escaped this time the best. Sir H. had his face cut in two places about the chin, and a violent blow on the forehead struck through a considerable thickness of silk and leather; and with this experiment he has for the present concluded."
Gattermann found the oil had the formula NCl3 only if the action of the chlorine gas was prolonged, as the chlorination of ammonia proceeds in three stages :
NH3 + Cl2 = NH2Cl (monochloramine) + HCl forms unstable & explosive colourless crystals at -66oC
NH2Cl + Cl2 = NHCl2 (dichloramine) + HCl
NHCl2 + Cl2 = NCl3 (trichloramine) + HCl
The 1929 Encyclopaedia Brittanica has this to say - "Nitrogen trichloride is a very dangerously explosive, volatile, yellow oil, boiling at 71oC. The vapour has a pungent odour and attacks the eyes and mucous membranes. The liquid explodes on contact with many substances or on exposure to bright light, but its solution in benzene may be safely handled in the dark. It is destroyed by ammonia."
Millon reacted nitrogen trichloride with potassium bromide -
NCl3 + 3KBr = NBr3 + 3KCl Nitrogen tribromide is a dark red, volatile, explosive oil.
These halogenated nitrogen oils are far too sensitive for any use as a practical explosive. Safe breakers had to wait until nitroglycerine was available to enable capillary action to fill the door to body seal and lock actions with explosive liquid -
Nitroglycerine is a very pale yellow oil. Ascanio Sobrero, in 1846, prepared C3H5(NO3)3 by the nitration of glycerine with a mixture of concentrated nitric and sulphuric acids.
In 1863, Alfred Nobel set up a factory near Stockholm, Sweden. He started producing nitroglycerine and began experimenting with the devilish liquid. In 1864 a quantity detonated at the laboratory, killing his brother Emil and four others. Town officials banned all further experimentation and his father had a stroke.
Maniacally undaunted, Nobel set up Nitroglycerin Ltd. It`s laboratory was situated on a barge in the middle of a lake, near the town. He strove to find a way of making this extremely powerful explosive more handleable and predictable. Meanwhile his countryside production facilities produced the oil by the bucketful. Much, much more powerful than blackpowder, "nitro" was in great demand, even considering it`s drawbacks....
A Pacific Mail Steamship unloaded it`s general merchandise onto a San Francisco wharf. Among the goods, a box appeared to be leaking. It was marked "Nobel`s Blasting Oil". The box was taken to the Wells Fargo office on California Street. Unaware of any danger and in order to investigate the leak, freight clerks used tools to open the box.
The nitroglycerine detonated at 1.15pm 16th April 1866. The Wells Fargo building, Bell`s assay office and the Union Club Rooms were all demolished. The ground shook quarter of a mile away. Windows shattered half a mile away.
The effect of the blast upon people is very graphically described by this account from the Auburn "Placer Herald" 21.4.1866
"In the auction room of Cobb and Sinton, on the east side of Montgomery Street, a human brain, almost intact, and other fragments of the body near it, were found. A piece of human vertebrae was blown over the buildings on the east side of Montgomery Street, where it was picked up in front of Squarza's, on Leidsdorff street. A piece of skull was lying on California Street, east of Leidsdorff, with other fragments of human remains, and a human arm struck the third story window of the building across the street."
With appalling incidents like the above happening, the pressure was on for Nobel to de-sensitise nitro. He succeeded in 1867, by mixing nitroglycerine with kieselguhr, a diatomaceous porous earth. The Sweat of the Devil was tamed, Dynamite had been invented and Nobel was on his way to becoming one of the world`s richest men.
PLEASE don`t attempt the manufacture of either of these oils. The danger, even to brilliant & experienced chemists, is not exaggerated. This page is for information only. No liability will be accepted for death, injury or damage arising from experimentation using any information presented here.