posted March 25, 2000 08:09 AM            

I have a question for you. What do you know about ethlynitrate (C2H5NO3)? I have read that
it can be made from 65% HNO3 and C2H5OH (i dont known how it is called in english maybe
ehtanole or simply alcohol) with urea as a catalyst for this reaction (so i think) by
distilling this mix. If it is so, how many urea should be used? And what about mixing
ethylnitate with ammonium nitrate to form ANNM like explosive? I know that it is impact
sensitive and that it would explode with Na etc. but what about its chemical stability?

Thanx,
petn

You could probably form a explosive slurry if you mixed it with Ammonium nitrate, since Ethyl nitrate is in the similar group of nitroglycerine (it's a nitric acid ester),
ethyl nitrate can be exploded but owns a detonation velocity lower than Methyl nitrate and nitroglycerine; Detonation velocity: 5,800m/s at density: 1.1g/cc, compared to Methyl nitrate: 6,300m/s at density: 1.217g/cc, Nitroglycerine 7700m/s at density 1.6g/cc.

Ethyl nitrate is flammable, more than ethanol. since Ethyl nitrate is like nitroglycerin, a nitric ester, water in the liquid wouldn't be to good to have in it. Ethyl nitrate is much less sensitive to initiation than methyl nitrate, so its shock-sensitivity won't be as high as methyl nitrate or nitroglycerine. A #8 Blasting cap will bring ethyl nitrate to detonation, unless the nitrate is tamped or confined. Mixed with fuller's earth in the proportion of 70/30 or 60/40, it yields a brisant explosive. But ethyl nitrate only has about 48% the energy content of nitroglycerine, and performs about 58% as well as nitroglycerin in the sand test.

Not:

The density of the nitric acid is 1.4g/ml, therefore 67% concentrated, but
65% should work also...

sorry, but the translation might be a BIT BAD!:

On pages 147-148 of the book mentioned, The preperation of Ethyl nitrate
is shown and also discussed. The procedure is as follows:

Ethyl nitrate

C2H5OH + HNO3 ---> C2H5ONO2 + H2O

250 ml conc. Nitric acid (d = 1.4) is boiled up with 30 g
(0.25 mol) Uronium nitrate (which basically is urea nitrate).
After cooling, one pours the half of the mixture in a dropping
funnel and descending cooler 1-Liter-flask, in which contain 30 g
(0.24 mol) Uronium nitrate and 150 ml 95% pure ethyl alcohol. The
flask is slowly heated on a sand- or oil bath at 120-130°C (Bath temperature.)
Wear Saftey goggles! After about 1/3 of this mixture has been destilled away,
mix the second half of the Nitric acid solution with 100 ml 95 % pure ethanol,
and let these mix slowly through the dropping funnel. The operation must be
carried out one another. And; the mixture of Ethanol and Nitric acid must
not be allowed to stand together for a long time (i already explained why, above).
When, all has been dripped to, and the liquid in the flask has been distilled away of
about 100 ml, one shakes the overgoing Ethyl nitrate for removal of the Ethanol
2 times with water, one time with dilute Sodum carbonate-solution
(CO2- is generated!) and then again, once with water (Ethyl nitrate is
heavier than water, so it will sink to the bottom), the product is then
dried with Calcium chloride and purify the product through distillation out of the
boiling water bath (Saftey goggles!), Yield 150-150 g (39-41%) Ethyl nitrate
with a boiling point of 86°C.

>>>Follow ALL instructions if anyone intends on making it, do not take
any guesses, or be ignorant about it. And make SURE you DRY the
Ethyl nitrate afterwards! Expose this material to drop weight tests,
etc. even though it is not as sensitive, expect the same hazards
as Nitroglycerin<<<

Ethyl nitrate decomposes with rapid heating, for example in the flame, explosively. It is
placed into the same class as Nitroglycerin, which oxidizing and reducing groups contain; therefore
Caution! One does not oxidize to ethyl alcohol by pure nitric acid ones under the leading conditions,
but it only esterifies. As soon as however tracks of more nitrous acid is present,
which are removed above by treating with urea, oxidation occurs by the NO2. Since the nitrogen
monoxide, which here from the nitrous acid develops, of which nitric acid ones again to NO2 one
oxidizes, the oxidation goes from small beginning gradually further, wins by the occurring reaction-warm
at rate and increases finally to a stubborn-mixed, Process like an explosion, One calls reaction accelerations
of this type, with which intermediate products increase the rate progressively, autocatalyses.

The first product of the oxidation of ethanol is acetaldehyde.
Later becomes underother one the level the fulminic acid HC=N->O achieved, which can be seized however only with
presence of silver- or mercury ions. With these it forms the barely soluble, against Nitric acid
resistant, against impact- and heat-sensitive fulminate (initial explosives).

German article:

Ethyl nitrat

C2H5OH + HNO3 ----> C2H5ONO2 + H2O

250 ml conc. Salpetersäure (d = 1,4) werden mit 30 g (0,25 mol) Uroniumnitrat
(Harnstoffnitrat!) aufgekocht. Nach dem Erkalten gießt man die Hälfte der Lösung
in einen mit Tropftrichter und absteigendem kühler versehenen 1-L-Kolben, in
dem sich 30 g (0,24 mol) Uroniumnitrat und 150 ml 95proz. Ethanol befinden. Der
Kolben wird auf einem Sand- oder in einem Ölbad langsam auf 120-130°C (Badtemp.)
erhitzt (Schutzbrille!). Nachdem etwa ein Drittel des Inhalts abdestilliert ist,
vermischt man die zweite Hälfte der Salpetersäurelösung mit 100 ml 95proz. Ethanol
und läßt diese Mishung durch den Tropftrichter langsam zufließen. Die Operation muß
hintereinander ausgeführt werden; die Gemische von Ethanol Salpetersäure dürfen nicht
längere Zeit stehen bleiben. Wenn, alles zugetropft und die Flüssigkeit im Kolben bis
auf etwa 100 ml abdestilliert ist, schüttelt man das übergegangene Ethylnitrat zur
Entfernung des Ethanols 2mal mit Wasser, einmal mit verd. Natriumcarbonat-Losung
(CO2-Entwicklung!) und dann nochmals mit Wasser aus (Ethylnitrat ist schwerer
als Wasser), trocknet uber Calciumchlorid und reinigt das Produkt durch
destillation aus dem siedenden Wasserbad (Schutzbrille!), Ausbeute 150-160 g
(39-41 %) Ethyl nitrat mit Sdp. 86°C.

Ethyl nitrat zersetzt sich beim raschen Erhitzen, zum Beispiel in der Flamme,
explosionsartig. Es gehört in die gleiche Klasse wie Nitroglycerin, die oxidierende und
reduzierende Gruppen enthält; darum Vorshicht! Ethylalkohol wird durch reine
Salpetersäure unter den voranstehenden Bedingungen nicht oxidiert, sondern nur
verestert. Sobald aber Spuren von salpetriger Säure vorhanden sind, die oben
durch die Behandelung mit Harnstoff entfernt werden, tritt durch das NO2
Oxidation ein. Da das Stickstoffmonoxid, das hierbei aus der salpetrigen Säure
ensteht, von der Salpetersäure wieder zu NO2 oxidiert wird, geht die Oxidation
von kleinen Anfängen sukzessive weiter, gewinnt durch die auftretende
Reaktionswarme an Geschwindigkeit und steigert sich schließlich zu einem
stürmischen, explosionsartigen Proceß. Reaktionsbeschleunigungen dieser Art,
bei denen Zwischenprodukte die Geschwindigkeit progressiv steigern , bezeichnet
man als Autokatalysen.
Das erste Produkt der Oxidation des Ethanols ist Acetaldehyd. Später wird unter
anderem die Stufe der Knallsäure HC=N->O erreicht, die aber nur bei Gegenwart
von Silber- oder Quecksilberionen gefaßt werden kann. Mit diesen bildet sie
die schwerlöslichen, gegen Salpetersäure beständigen, gegen Schlag und Hitze
empfindlichen Fulminate (Initialzünder).

With mercury it was different, simply adding mercury to a strong solution of HNO3 (98% fuming) caused it to dissolve very quickly, with the generation of the toxic NO2 fumes.

Here's an interesting article from "The Chemistry of Powder & Explosives":
(About the mercury fulminate forming.)

The chemical reactions in the preperation appear to be as follows. (1) The alcohol is oxidized to acetaldehyde, and (2) the nitrous acid (from nitric oxide and nitrogen dioxide formed that react with the moisture to from HNO2.) which is formed attacks the acetaldehyde to form a nitroso deriative which goes over to the more stable, tautomeric, isonitroso form.

CH3-CH2-OH --> CH3-CHO ----->
CH2-NO-CHO (Nitrosoacetaldehyde) <-- -->
CH=N-OH-CHO (Isonitrosoacetaldehyde)

(3) The isonitrosoacetaldehyde is oxidized to isonitrosoacetic acid, and (4) this is nitrated by the nitrogen dioxide which is present to form nitroisonitrosoacetic acid.

CH=N-OH-CHO ---> CH=N-OH-COOH (Isonitrosoacetic acid) ---> C-NO2-COOH=N-OH (Nitroisonitrosoacetic acid)

(5) The nitroisonitrosoacetic acid loses carbon dioxide to form formonitrolic acid which (6) decomposes further into nitrous acid and fulminic acid, and (7) the fulminic acid reacts with the mercury nitrate to form the sparingly soluble mercury fulminate which precipitates.

NO2-C=N-OH-COOH ---> NO2-CH=N-OH (Formonitrolic acid) ----> HONC --->
Hg (ONC)2 (Mercury fulminate)