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Alkoholvergiftung
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See Attachment. They are in German.
Attachment: NitritDE000000168450A_2.pdf (65kB)
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Alkoholvergiftung
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First Part.
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Lionel Spanner
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Quote: Originally posted by unionised  |
Am I reading this correctly? The yield is about 50 micro moles per square cm per week.
So, with a 10cm by 10 cm electrode you would get less than a quarter of a gram of nitrite per week.
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That's with 0.1 molar ammonia, i.e. 0.17% w/v. I suspect a more concentrated solution would result in better yields.
[Edited on 22-8-2023 by Lionel Spanner]
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Alkoholvergiftung
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I ve found this crusicible methode.Englisch and later german copy.
Very finely divided metallic copper is first prepared by distillation of acetate of copper, and from this freshly prepared metallic powder, 2
equivalents, or even a slight excess, are taken to 1 equivalent of nitrate, according to the equation
2 Cu + KO, NO⁵ = 2 CuO + KO, NO³.
Persoz took 320 grm. saltpetre and 200 grm. from the copper represented in the manner indicated.
To prepare an intimate mixture, the saltpeter is first dissolved in the smallest possible quantity of hot water, and then the copper is added, which
at first is difficult to wet. When the mixture has become quite uniform, it is heated in a porcelain dish, or better yet, in a cast-iron pan, in a
sand bath, stirring constantly to prevent splashing. When the mass is completely dry, there comes a moment when, like a pyrophor, it catches fire and
glows; when the combustion is over, which lasts but a moment, the reaction has taken place; it is allowed to cool, the melt treated with water,
filtered, and the nitrate allowed to crystallize. If excess copper has been used, no nitrate is present, and crystallized nitrite is obtained at once,
which is then melted and kept in well-closed flasks, as the salt is very hygroscopic. Any undecomposed nitrate of potash present is separated out by
the first crystallization, since it is far less soluble than nitrate of potash. The copper oxide obtained as a residue during the operation can, after
proper washing, be used for organic analysis, or at least for mixing with the organic substance to be examined, since, although it is very finely
divided, it is nevertheless very dense and to a much lesser degree hygroscopic than the annealing of nitrate of copper.
It is to be remarked, however, that common copper, even in a very finely divided form, would not be fit for the foregoing purpose, as in its
application
to bring about the intended reaction the temperature would have to be raised much higher, so that caustic potash rather than nitrate of potash would
be obtained; on the other hand, when using the copper prepared from the acetate salt, the reaction occurs at as little as 200° to 250° C. (Annales
du Conservatoire des arts et métiers, t. II p. 353.)
Man bereitet sich zunächst durch Destillation von essigsaurem Kupferoxyd sehr fein zertheiltes metallisches Kupfer, und nimmt von diesem frisch
bereiteten Metallpulver 2 Aequivalente oder selbst einen geringen Ueberschuß, auf 1 Aequivalent Salpeter, entsprechend der Gleichung
2 Cu + KO, NO⁵ = 2 CuO + KO, NO³.
Persoz nahm 320 Grm. Salpeter und 200 Grm. von dem auf die angegebene Weise dargestellten Kupfer.
Zur Herstellung eines innigen Gemenges löst man den Salpeter zunächst in der möglich geringsten Menge heißen Wassers, und setzt dann das Kupfer
hinzu, welches sich anfänglich nur schwierig benetzen läßt. Ist das Gemenge recht gleichartig geworden, so erhitzt man dasselbe in einer
Porzellanschale oder besser, in einer gußeisernen Pfanne im Sandbade unter beständigem Umrühren, um Spritzen zu verhüten. Ist die Masse
vollständig getrocknet, so tritt ein Moment ein, wo sie, gleich einem Pyrophor, Feuer fängt und erglüht; ist die Verbrennung vorüber, was nur
einen Augenblick dauert, so hat die Reaction stattgefunden; man läßt erkalten, behandelt die Schmelze mit Wasser, filtrirt und läßt das
salpetrigsaure Salz krystallisiren. Hat man überschüssiges Kupfer angewendet, so ist kein Nitrat vorhanden und man erhält sogleich krystallisirtes
Nitrit, welches man dann schmilzt und in gut verschlossenen Flaschen aufbewahrt, da das Salz sehr hygroskopisch ist. Etwa vorhandenes nicht zersetztes
salpetersaures Kali wird durch die erste Krystallisation abgeschieden, da es weit weniger löslich ist als das salpetrigsaure Kali. Das bei der
Operation als Rückstand erhaltene Kupferoxyd kann nach gehörigem Auswaschen zur organischen Analyse, wenigstens zum Vermengen mit der zu
untersuchenden organischen Substanz angewendet werden, da es, obgleich sehr fein zertheilt, dennoch sehr dicht und in weit geringerem Grade
hygroskopisch ist, als das durch Glühen von salpetersaurem Kupferoxyd erhaltene.
Zu bemerken ist indessen, daß gewöhnliches Kupfer, selbst in sehr fein zertheilter Form, zu dem vorstehenden Zwecke sich nicht eignen würde, da bei
seiner Anwendung
zur Hervorrufung der beabsichtigten Reaction die Temperatur weit höher gesteigert werden müßte, so daß man eher Aetzkali als salpetrigsaures Kali
erhalten würde; bei Anwendung des aus dem essigsauren Salze dargestellten Kupfers hingegen tritt die Reaction schon bei 200 bis 250° C. ein.
(Annales du Conservatoire des arts et métiers, t. II p. 353.)
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woelen
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Interesting quote. The english translation contains some small, but essential errors. Below follows the corrected translation.
Very finely divided metallic copper is first prepared by distillation of acetate of copper, and from this freshly prepared metallic powder, 2
equivalents, or even a slight excess, are taken to 1 equivalent of saltpeter, according to the equation
2 Cu + KO, NO⁵ = 2 CuO + KO, NO³.
Persoz took 320 grm. saltpeter and 200 grm. from the copper represented in the manner indicated.
To prepare an intimate mixture, the saltpeter is first dissolved in the smallest possible quantity of hot water, and then the copper is added, which
at first is difficult to wet. When the mixture has become quite uniform, it is heated in a porcelain dish, or better yet, in a cast-iron pan, in a
sand bath, stirring constantly to prevent splashing. When the mass is completely dry, there comes a moment when, like a pyrophor, it catches fire and
glows; when the combustion is over, which lasts but a moment, the reaction has taken place; it is allowed to cool, the melt treated with water,
filtered, and the nitrite allowed to crystallize. If excess copper has been used, no nitrate is present, and
crystallized nitrite is obtained at once, which is then melted and kept in well-closed flasks, as the salt is very hygroscopic. Any undecomposed
nitrate of potash present is separated out by the first crystallization, since it is far less soluble than nitrite of
potash. The copper oxide obtained as a residue during the operation can, after proper washing, be used for organic analysis, or at least for mixing
with the organic substance to be examined, since, although it is very finely divided, it is nevertheless very dense and to a much lesser degree
hygroscopic than the annealing of nitrate of copper.
It is to be remarked, however, that common copper, even in a very finely divided form, would not be fit for the foregoing purpose, as in its
application to bring about the intended reaction the temperature would have to be raised much higher, so that caustic potash rather than nitrite of potash would be obtained; on the other hand, when using the copper prepared from the acetate salt, the reaction
occurs at as little as 200° to 250° C. (Annales du Conservatoire des arts et métiers, t. II p. 353.)
This is quite an interesting thing. I did not know that copper acetate can be converted to copper metal by heating the salt. This is definitely
something to try on a small scale. Maybe this process also works with NaNO3 instead of KNO3. The resulting NaNO2 is much less hygroscopic than KNO2.
Also interesting to see that in this old writing potassium ion is considered divalent. They wrote KO,NO5 for potassium nitrate, which we now would
write as K(NO3)2. Potassium nitrite is KO,NO3, which in modern notation would be K(NO2)2. Copper(II) at that time already was regarded as a divalent
ion.
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Alkoholvergiftung
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It was from 1864.So the lag of knowlege.
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woelen
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This kind of old information can be really interesting. I believe that in old books and papers there is a lot of interesting information about common
compounds, which is totally forgotten nowadays. This is exactly, why I love to read old books from around 1900 or so.
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unionised
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| Quote: Originally posted by Lionel Spanner | | Quote: Originally posted by unionised |
Am I reading this correctly? The yield is about 50 micro moles per square cm per week.
So, with a 10cm by 10 cm electrode you would get less than a quarter of a gram of nitrite per week.
|
That's with 0.1 molar ammonia, i.e. 0.17% w/v. I suspect a more concentrated solution would result in better yields.
[Edited on 22-8-2023 by Lionel Spanner] |
I suspect that a higher NH3 concentration would increase the yield of N2 at the expense of NO2- ions.
And the reasons for my suspicion are the law of mass action and the instability of ammonium nitrite.
But, until someone does the experiment, we won't know.
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unionised
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This tells you more than you probably want to know about decomposing copper acetate.
https://www.scirp.org/journal/paperinformation.aspx?paperid=...
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Fantasma4500
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Major success- breakthrough
| Quote: Originally posted by woelen |
Very finely divided metallic copper is first prepared by distillation of acetate of copper, and from this freshly prepared metallic powder, 2
equivalents, or even a slight excess, are taken to 1 equivalent of saltpeter, according to the equation
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you think thats an interesting quote? this is a marvellous breakthrough in nitrite preparation. i just tried it, mixed 3.2g KNO3 with 3.2g copper
sponge i made from copper-copper electrolysis, NaCl + .. 1-3% HCl?
i believe CuCl2 + Al would also give copper fine enough for this
i folded up some aluminium foil and heated the mixture with a blowtorch until it melted and torched the top as well, maybe 5 seconds, it glowed from
the flame
dipped that into 10mL water and shook it until the solid came off, black solid
it dissolved effectively, good sign. a few mL IPAlcohol in, a squirt of 10% H2SO4 and both vasodilatory + flame test proved success, i only took maybe
100mg sample to torch
no need for copper acetate decomposition, electrolytic copper sponge is plenty fine
a chemist proposed that Cu2O may also work, but that only makes sense if we can make Cu2O very easily.. CuCl2 + Al goes quite fast especially if you
can dump in a bunch of ice as well to keep it under control
this reaction should go very well with a hotplate and pot ontop, metal crucible, insulated with aluminium wool
edit: NaNO3 works too
[Edited on 28-8-2023 by Fantasma4500]
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Alkoholvergiftung
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FeO very fine should work too.
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Fantasma4500
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FeO is made from iron oxalate, i already tried NaNO3 + iron oxalate heated together, poor results
copper powder works. its solved.
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clearly_not_atara
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You inhaled crude isopropyl nitrite?!
Well, I guess we know it works...
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Fantasma4500
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well, i tasted sodium cyanide too, bitter taste stuck 30 mins, tongue numb 2 weeks
chloroform, tastes nice and sweet
accidentally inhaled HF while doing silversolderings, strongly acidic smell, and boron trifluoride
dived into a thick fog of SO3
walked through a fog of Cu/CuO
tremors from nickel poisoning
acquired a diabolic headache lasting hours by taking a single drop of 10% EGDN in acetone and placing on my arm
a slight vasodilation from IPNitrite is not something to worry about.
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Alkoholvergiftung
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I hope you never try this methode on mercury compounds.
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Fantasma4500
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reporting grand success with electrolytic copper and NaNO3, 120g + 120g copper, heated together at about 400*C for an hour in closed container, black
lowdensity crumbling spongy material achieved
120g NaNO3 used, 100g in 400mL H2O acquired, theoretically 120g NaNO3 turns into 97g NaNO2
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Alkoholvergiftung
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to bad if it was closed maybe it reacts like stated at 200-250C exotherm. Would much easier to reach with an hotplate.
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Fantasma4500
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reporting in that Cu2O also works quite well, may even work better than copper metal
CuO is widely available, Cu2O was made by reacting solution of ascorbic acid with heating with CuO which i acquired from previous Cu + NaNO3 run,
looking for alternatives to ascorbic acid as HCl + CuO + Al is also very easy, and aluminium in that case is the reducing agent
CuO and Cu2O is roughly same price, onyxmet lists Cu2O as 4.00 euros where CuO is 3.75 euro for 10 grammes
1188g KNO3 + 1681g Cu2O = 1000g KNO2 + 1869g CuO
CuO seems possible to reduce with sugar and some salt like sodium citrate and copper sulfate, maybe glucose and sodium hydroxide?
[Edited on 2-9-2023 by Fantasma4500]
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Rainwater
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| Quote: Originally posted by Fantasma4500 | reporting grand success with electrolytic copper and NaNO3, 120g + 120g copper, heated together at about 400*C for an hour in closed container, black
lowdensity crumbling spongy material achieved
120g NaNO3 used, 100g in 400mL H2O acquired, theoretically 120g NaNO3 turns into 97g NaNO2
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How was the product isolated for yield measurement?
"You can't do that" - challenge accepted
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Fantasma4500
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| Quote: Originally posted by Rainwater | | Quote: Originally posted by Fantasma4500 | reporting grand success with electrolytic copper and NaNO3, 120g + 120g copper, heated together at about 400*C for an hour in closed container, black
lowdensity crumbling spongy material achieved
120g NaNO3 used, 100g in 400mL H2O acquired, theoretically 120g NaNO3 turns into 97g NaNO2
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How was the product isolated for yield measurement? |
well its a very clean reaction and zero nitrate is claimed by wolens reference, barely any "gunpowder" smell detectable inside the reaction vessel
after a whole hour of operating, seeing that after i heated a 10mL solution sample in oven for an hour with fan going, and there was still aggressive
amounts of nitrite in it, i wager that i have a solution is quite pure sodium nitrite, i could maybe get a bit extra scientific with using silver
nitrate to precipitate it out but im okay with just believing its pure enough for my desires. its a very easy reaction so i invite anyone else more
eager for data to repeat it, also for the sake of science and replication
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Lionel Spanner
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Below is a useful quantitative assay I've used in the past for testing the purity of nitrite.
1. Weigh accurately about 1.0 g of the sample of sodium or potassium nitrite to be assayed into a 250 mL volumetric flask, and record the weight (W).
2. Fill the flask about halfway with deionised water, and mix until all solids are dissolved.
3. Once all solids are dissolved, make up to the mark with deionised water.
4. Weigh 5% sulphuric acid (75 g) into a 250 mL conical flask.
5. Add 0.02M (0.1N) potassium permanganate solution (25 mL) to the conical flask via a pipette.
6. Titrate the contents of the flask with the nitrite solution. The end point is reached when the mixture just goes colourless; record the volume of
solution delivered (T).
7. The % purity of the assayed sample can be determined by the following equation:
%P = 2156.25 ÷ T ÷ W (for sodium nitrite)
%P = 2626.25 ÷ T ÷ W (for potassium nitrite)
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Fantasma4500
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just wanted to add CuO as from the reduction reaction can be reduced to Cu2O using glucose and NaOH, boiled for a few hours
the Cu2O reacts with HCl to form a water soluble salt which is black, upon dilution it becomes CuCl, this is the washed and dried Cu2O so no reducing
agents leftover in it, cool little bonus.
100g NaNO3 needs 160ish Cu2O, NaOH or H2SO4 may be used to turn sucrose into glucose with heating in solution, straight up glucose seemed to work
better tho, ascorbic acid works very well but not as OTC.
KNO3 seems dreadful for making nitrite for some reason, mostly didnt react with some of the copper powder i used, NaNO3 seems much better- probably
because its just a bit more reactive
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Kevlar
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I've read this 21 year long thread and deduced one thing, that by far the best method I have seen is a displcement method -
(Ca(NO3)2) + (Na2SO4), The balanced equation is:
Ca(NO3)2 + Na2SO4 → CaSO4 + 2NaNO3
The stoichiometry of the reaction is a nice 1:1 ratio in moles, both of the chemicals are OTC and cheap & the end clean product being pure 2NaNO3.
Which is easy to sep from the insoluable CaSO4.
I will buy some of both and come back with pictures, I have got a ref sample of the 2NaNO3 to compare with.
I have been saving up a lot of eggshells and might make the Ca(Na3)2 along with the nitric acid from KaO3 + NaCl reaction.
“If you do not expect the unexpected, you will not find it, for it is not to be reached by search or trail.”
(Heraclitus)
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fx-991ex
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We trying to make nitrite NO2 not nitrate NO3.
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Kevlar
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fx-991ex I will make the NaO2 from oxidation of the NaO3 using starch, I just got carried away with doing some inorganic chem.
But thanks for pointing that out to me!
“If you do not expect the unexpected, you will not find it, for it is not to be reached by search or trail.”
(Heraclitus)
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