Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
 Pages:  1  ..  14    16
Author: Subject: Preparation of ionic nitrites
Alkoholvergiftung
Hazard to Others
***




Posts: 151
Registered: 12-7-2018
Member Is Offline


[*] posted on 21-8-2023 at 07:32


See Attachment. They are in German.

Attachment: NitritDE000000168450A_2.pdf (65kB)
This file has been downloaded 165 times
View user's profile View All Posts By User
Alkoholvergiftung
Hazard to Others
***




Posts: 151
Registered: 12-7-2018
Member Is Offline


[*] posted on 21-8-2023 at 07:33


First Part.

Attachment: NitritDE000000168450A_1 (1).pdf (78kB)
This file has been downloaded 171 times

View user's profile View All Posts By User
Lionel Spanner
Hazard to Others
***




Posts: 163
Registered: 14-12-2021
Location: near Barnsley, UK
Member Is Offline


[*] posted on 22-8-2023 at 06:11


Quote: Originally posted by unionised  
Quote: Originally posted by Parakeet  
Here it is.
Haven't read everything yet, but the procedure looks amateur friendly.


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]




Industrial chemist rediscovering the practical pleasures of pure chemistry.
Sometimes I make videos - https://www.youtube.com/@yorkshirechemist
View user's profile View All Posts By User
Alkoholvergiftung
Hazard to Others
***




Posts: 151
Registered: 12-7-2018
Member Is Offline


[*] posted on 24-8-2023 at 04:50


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.)
View user's profile View All Posts By User
woelen
Super Administrator
*********




Posts: 7976
Registered: 20-8-2005
Location: Netherlands
Member Is Offline

Mood: interested

[*] posted on 24-8-2023 at 05:11


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.




The art of wondering makes life worth living...
Want to wonder? Look at https://woelen.homescience.net
View user's profile Visit user's homepage View All Posts By User
Alkoholvergiftung
Hazard to Others
***




Posts: 151
Registered: 12-7-2018
Member Is Offline


[*] posted on 24-8-2023 at 06:07


It was from 1864.So the lag of knowlege.
View user's profile View All Posts By User
woelen
Super Administrator
*********




Posts: 7976
Registered: 20-8-2005
Location: Netherlands
Member Is Offline

Mood: interested

[*] posted on 24-8-2023 at 23:14


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.



The art of wondering makes life worth living...
Want to wonder? Look at https://woelen.homescience.net
View user's profile Visit user's homepage View All Posts By User
unionised
International Hazard
*****




Posts: 5102
Registered: 1-11-2003
Location: UK
Member Is Offline

Mood: No Mood

[*] posted on 25-8-2023 at 05:36


Quote: Originally posted by Lionel Spanner  
Quote: Originally posted by unionised  
Quote: Originally posted by Parakeet  
Here it is.
Haven't read everything yet, but the procedure looks amateur friendly.


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.
View user's profile View All Posts By User
unionised
International Hazard
*****




Posts: 5102
Registered: 1-11-2003
Location: UK
Member Is Offline

Mood: No Mood

[*] posted on 25-8-2023 at 06:25


This tells you more than you probably want to know about decomposing copper acetate.

https://www.scirp.org/journal/paperinformation.aspx?paperid=...
View user's profile View All Posts By User
Fantasma4500
International Hazard
*****




Posts: 1677
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline

Mood: dangerously practical

shocked.gif posted on 27-8-2023 at 11:30
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


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]




~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
http://www.trimen.pl/witek/calculators/stezenia.html
View user's profile View All Posts By User
Alkoholvergiftung
Hazard to Others
***




Posts: 151
Registered: 12-7-2018
Member Is Offline


[*] posted on 28-8-2023 at 00:06


FeO very fine should work too.
View user's profile View All Posts By User
Fantasma4500
International Hazard
*****




Posts: 1677
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline

Mood: dangerously practical

[*] posted on 28-8-2023 at 10:02


Quote: Originally posted by Alkoholvergiftung  
FeO very fine should work too.


FeO is made from iron oxalate, i already tried NaNO3 + iron oxalate heated together, poor results
copper powder works. its solved.




~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
http://www.trimen.pl/witek/calculators/stezenia.html
View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 2691
Registered: 3-11-2013
Member Is Offline

Mood: Big

[*] posted on 28-8-2023 at 13:46


You inhaled crude isopropyl nitrite?!

Well, I guess we know it works...




[Edited on 04-20-1969 by clearly_not_atara]
View user's profile View All Posts By User
Fantasma4500
International Hazard
*****




Posts: 1677
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline

Mood: dangerously practical

[*] posted on 29-8-2023 at 13:08


Quote: Originally posted by clearly_not_atara  
You inhaled crude isopropyl nitrite?!

Well, I guess we know it works...


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.




~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
http://www.trimen.pl/witek/calculators/stezenia.html
View user's profile View All Posts By User
Alkoholvergiftung
Hazard to Others
***




Posts: 151
Registered: 12-7-2018
Member Is Offline


[*] posted on 30-8-2023 at 05:39


I hope you never try this methode on mercury compounds.
View user's profile View All Posts By User
Fantasma4500
International Hazard
*****




Posts: 1677
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline

Mood: dangerously practical

[*] posted on 1-9-2023 at 07:25


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





~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
http://www.trimen.pl/witek/calculators/stezenia.html
View user's profile View All Posts By User
Alkoholvergiftung
Hazard to Others
***




Posts: 151
Registered: 12-7-2018
Member Is Offline


[*] posted on 2-9-2023 at 04:49


to bad if it was closed maybe it reacts like stated at 200-250C exotherm. Would much easier to reach with an hotplate.
View user's profile View All Posts By User
Fantasma4500
International Hazard
*****




Posts: 1677
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline

Mood: dangerously practical

[*] posted on 2-9-2023 at 05:34


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]




~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
http://www.trimen.pl/witek/calculators/stezenia.html
View user's profile View All Posts By User
Rainwater
National Hazard
****




Posts: 799
Registered: 22-12-2021
Member Is Offline

Mood: indisposition to activity

[*] posted on 2-9-2023 at 06:40


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


How was the product isolated for yield measurement?




"You can't do that" - challenge accepted
View user's profile View All Posts By User
Fantasma4500
International Hazard
*****




Posts: 1677
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline

Mood: dangerously practical

[*] posted on 4-9-2023 at 06:16


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


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




~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
http://www.trimen.pl/witek/calculators/stezenia.html
View user's profile View All Posts By User
Lionel Spanner
Hazard to Others
***




Posts: 163
Registered: 14-12-2021
Location: near Barnsley, UK
Member Is Offline


[*] posted on 5-9-2023 at 07:57


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)




Industrial chemist rediscovering the practical pleasures of pure chemistry.
Sometimes I make videos - https://www.youtube.com/@yorkshirechemist
View user's profile View All Posts By User
Fantasma4500
International Hazard
*****




Posts: 1677
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline

Mood: dangerously practical

[*] posted on 7-9-2023 at 01:17


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




~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
http://www.trimen.pl/witek/calculators/stezenia.html
View user's profile View All Posts By User
Kevlar
Harmless
*




Posts: 16
Registered: 5-2-2024
Location: UK
Member Is Offline


[*] posted on 9-3-2024 at 02:21


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)
View user's profile View All Posts By User
fx-991ex
Hazard to Self
**




Posts: 67
Registered: 20-5-2023
Member Is Offline


[*] posted on 9-3-2024 at 05:34


We trying to make nitrite NO2 not nitrate NO3.
View user's profile View All Posts By User
Kevlar
Harmless
*




Posts: 16
Registered: 5-2-2024
Location: UK
Member Is Offline


[*] posted on 10-3-2024 at 03:38


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)
View user's profile View All Posts By User
 Pages:  1  ..  14    16

  Go To Top