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Author: Subject: Cheapest Hydroxylamine
TEK
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Cheapest Hydroxylamine

What place has the cheapest hydroxylamine hcl? If anyone on here wants to sell any send me a U2U.

[Edited on 4-8-2009 by TEK]
Formula409
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Formula409.
Siddy
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Is there away to easily separate the formic acid from that mix?

Saturate with hydroxide salt and boil/evap hydroxylamine (decomp) and water?
Picric-A
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add to water to crystalise out the salt crystals
Siddy
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how, when formate salts are typically VERY soluble?
starman
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Hydroxylamine can also be produced by the reduction of nitrous acid or potassium nitrate with bisulfite:

HNO2 + 2 HSO3− → N(OH)(OSO2)22− + H2O → NH(OH)(OSO2)− + HSO4−
NH(OH)(OSO2)− + H3O+ (100 °C/1 h) → NH3(OH)+ + HSO4−

I was wondering if anyone had come across a detailed preparation of this route.

Chemistry- The journey from the end of physics to the beginning of life.(starman)
ammonium isocyanate
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You can get it at http://www.photoformulary.com/DesktopDefault.aspxtabindex=2&... but at 16.25 for 100g it's not exactly cheap but not too bad either. Not sure what their shipping policy is though.

S.C. Wack
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 Quote: Originally posted by starman Hydroxylamine can also be produced by the reduction of nitrous acid or potassium nitrate

Nitrate = fail
Brauer = win (a useful potassium salt).
Formula409
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 Quote: Originally posted by starman I was wondering if anyone had come across a detailed preparation of this route.

Here we go:
http://www.erowid.org/archive/rhodium/chemistry/hydroxylamin...
http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0318

Formula409.
S.C. Wack
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He used the word bisulfite and I assumed that this meant bisulfite, the actual salt; not in situ - which are a dime a dozen in the literature.
Sedit
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The second reference in the paper is stated to use Sodium Bisulfite and Sodium Nitrite solutions S.C.

Reference: Raschig, Ann. 241, 161 (1887); Ger. pat. 41,987 [Chem. Zentr. I, 246 (1888)]; Divers and Haga, J. Chem. Soc. 69, 1665 (1896); 77, 673 (1900); Adams and Kamm, J. Am. Chem. Soc. 40, 1281 (1918).

The other reference Raschig, Ger. pat. 216,747 [Chem. Zentr. I, 308 (1910)] is mentioned to use Calcium nitrite inorder to precipitate the formed Calcium Sulfate from the solution with ease.

Im going to attempt to find these papers as I have the desire to attempt the former process and see how effective it is.

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S.C. Wack
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 Quote: Originally posted by Sedit The second reference in the paper is stated to use Sodium Bisulfite and Sodium Nitrite solutions S.C.

Yeah I can read, and am aware of this "Organic Syntheses" thing. The only one of those that actually has a procedure for using solid bisulfite, is Rachig...and guess whose article is translated to English in Brauer. I tend to write with care.

I was just trying to point out that all other literature procedures make sodium bisulfite, while the one in Brauer uses it.
Sedit
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My fault, I thought you where making mention to looking for one that uses the salt instead of insitu production. You don't by anychance have that paper on hand do you since I am quite interested in seeing some experimental details of it. I have not had the time to look for it just yet but will do so in a bit.

Knowledge is useless to useless people...

"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story before."~Maynard James Keenan
starman
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mmm - Interesting gentlemen.Just happen to have some calciuim nitrite,but not access to Brauer. I think I'll take a peek at the DE patent.

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entropy51
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 Quote: Originally posted by starman mmm - Interesting gentlemen.Just happen to have some calciuim nitrite,but not access to Brauer. I think I'll take a peek at the DE patent.
Isn't Brauer in the Forum library????
DJF90
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Yup.
starman
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Whoops. I'm going to translate the example section of the DE patent anyways.Dust off the high school german.

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EmmisonJ
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 Quote: Originally posted by ammonium isocyanate You can get it at http://www.photoformulary.com/DesktopDefault.aspxtabindex=2&... but at 16.25 for 100g it's not exactly cheap but not too bad either. Not sure what their shipping policy is though.

they sell the sulfate but he's looking for the hcl salt. wouldn't it be easier to do like ammonium isocyanate says and buy the sulfate then convert it to the hcl salt? i'm not too familiar with hydroxylamine i'm curious if a simple a/b would work? not sure about it's solubility in water in these various salt forms. it also seems that it's pretty volatile and would melt into a gas at a few degrees above room temp. it would probably be best to play on its solubility to keep it solvated throughout the process. does anyone know a good way to go about converting the sulfate to the hcl salt in this case?

[Edited on 3-10-2009 by EmmisonJ]
Theophrastus_2
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Actually, I know that some stores sell racing fuel for cars, that is composed purely of nitromethane, solvated in methanol, and costs something around $16 per Litre (/ 1.5 litres; I'm not exactly sure). Addition of hydrochloric acid to the nitromethane solution, would then give you the intended hydroxylamine hydrochloride. Out of interest, I'm pretty sure that formic acid would be miscible with methanol, but how soluble in contrast, is hydroxylamine hydrochloride in methanol? I sometimes use good amounts of miscible organics, in order to precipitate and induce crystalization in substances, however, I've only used acetone yet. When I get some racing fuel, I'll see how I'll have to extract the hydroxylamine hydrochloride, but as I said, that may take a fair while. Until then, does anyone have some empirical evidence on the matter? -Theo UnintentionalChaos International Hazard Posts: 1454 Registered: 9-12-2006 Location: Mars Member Is Offline Mood: Nucleophilic  Quote: Originally posted by Theophrastus_2 Actually, I know that some stores sell racing fuel for cars, that is composed purely of nitromethane, solvated in methanol, and costs something around$16 per Litre (/ 1.5 litres; I'm not exactly sure). Addition of hydrochloric acid to the nitromethane solution, would then give you the intended hydroxylamine hydrochloride. Out of interest, I'm pretty sure that formic acid would be miscible with methanol, but how soluble in contrast, is hydroxylamine hydrochloride in methanol? I sometimes use good amounts of miscible organics, in order to precipitate and induce crystalization in substances, however, I've only used acetone yet. When I get some racing fuel, I'll see how I'll have to extract the hydroxylamine hydrochloride, but as I said, that may take a fair while. Until then, does anyone have some empirical evidence on the matter? -Theo

One of the published procedures we have here details a simple pressure reactor to carry out hydrolysis of nitromethane. I'm under the impression that it does not proceed readily at room temp or even reflux.

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I na synthesis of dimethylglyoxime, I produced a solution of hydroxylamine in water by reacting sodium bisulfite with sodium nitrite in a slightly acid ic solution. The solution turns quite dark in color and the temperature has to be carefully controlled. The biacetyl monoxime is then added to the hydroxylamine solution and the mixture was brought to a boil and filtered. After cooling for several hours in an ice bath, large quantities of dimethylglyoxime formed. This was filtered off and dried. The product melted at 245 degrees Celsius and was obtained in a yeild of around 40% based on 2-butanone. This procedure was adapted from Vogel and Organic Syntheses. This should be applicable to water soluble ketones. I have tired to synthesize hydroxylamine hydrochloride several times with little success. The hydroxylamine hydrochloride could be obtained from the solution by forming acetoxime with acetone, steam distilling the oxime, hydrolyzing the oxime with hydrochloric acid and then concentration to obtain the hydroxylamine hydrochloride.

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Picric-A
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Must you use an exess of bisulphite becuase hydroxylamine reacts with sodium nitrite releasing nitrous oxide
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Quote: Originally posted by EmmisonJ
 Quote: Originally posted by ammonium isocyanate You can get it at http://www.photoformulary.com/DesktopDefault.aspxtabindex=2&... but at 16.25 for 100g it's not exactly cheap but not too bad either. Not sure what their shipping policy is though.

they sell the sulfate but he's looking for the hcl salt. wouldn't it be easier to do like ammonium isocyanate says and buy the sulfate then convert it to the hcl salt? i'm not too familiar with hydroxylamine i'm curious if a simple a/b would work? not sure about it's solubility in water in these various salt forms. it also seems that it's pretty volatile and would melt into a gas at a few degrees above room temp. it would probably be best to play on its solubility to keep it solvated throughout the process. does anyone know a good way to go about converting the sulfate to the hcl salt in this case?

[Edited on 3-10-2009 by EmmisonJ]

Use calcium chloride for a simple displacement,precipitating calcium sulfate.Purification can make use of the fact that hydroxylamine HCl is far more soluble in organic solvents than the sulfate.

Chemistry- The journey from the end of physics to the beginning of life.(starman)
EmmisonJ
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i've read a few different msds but was curious on a couple practical aspects of hydroxylamine. it seems that hydroxylamine isn't alarmingly toxic, but it is explosive and that is really the only concern with handling it but that is in reference to the freebase form.

1. what about how explosive is the salt form? any other concerns?
2. also what about proper storage of the hcl salt form? basically two choices for storage are available - a non-air-conditioned room that gets 100+F in the summer or in the freezer.
3. how long can hydroxylamine hcl be stored without worry about decomposition? is it like hydroquinone and MeAm HCl in the sense that if stored properly they will basically be fine for decades? i see it's hygroscopic and must be kept dry and also must not get heated to its decomposition temp of ~155C (or 17C when dissolved in water, apparently it decomposes readily in water?)
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1.) Its salt is definitely safe to work with, unless you want to heat it dry or perhaps with a flame (both general no-no's anyway).
2.) Doesn't matter. Just don't open hygroscopic reagents while the bottle's still cold (condenses water).
3.) Quite a long time. Ammonium salts (hydrochlorides especially) are not prone to oxidation, and thus can be stored almost indefinitely. And it doesn't decompose 'readily' in water. Most reactions involving hydroxylamine, however, are nonetheless not carried out in water.

I would consider it comparable to ammonium chloride. Nothing to be overly concerned about. Since you can't really buy hydroxylamine free-base, and you generally make it <i>in situ</i> it's really not a cause for concern. Explosive and flammable things are (generally) well behaved in solution.

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