Sciencemadness Discussion Board

NH4ClO3, Ammonium chlorate synthesis

plante1999 - 24-2-2012 at 14:23

I tried to make Ammonium chlorate as an intermediate for chloric acid production. Heating NH4ClO3 with Ca(OH)2 will yield Ca(ClO3)2 and NH3 gas.A solution of Ca(ClO3)2 could then be reacted with H2SO4 to make Insolube CaSO4 and a solution of HClO3.

Abstract:

Here is documented a simple and safe way to synthesise NH4ClO3 from easy to find reagents and using minimal amount of glassware. The process is reliable and fast. The product is somewath pure but contaminated with sodium ion, A recrystallisation give much better purity without sodium ion contamination. General use of NH4ClO3 are: Making Barium chlorate from Barium carbonate and NH4ClO3 and making HClO3.



Reagent:

NH4NO3, Ammonium nitrate 99%(approx) from high quality instant cold pack (5$ for 40g)

NaClO3, Sodium Chlorate 98-99%(approx) from electrolysis and recrystallised twice

H2O, Distilled water (Unknow purity) from grocery store

Material:

Beaker, 50ml, Glass, brand: Pyrex classic

Funnel, 50mm, HDPE, brand: dollar store

Coffee filter, brand: Sélection mérite



Equation of the reaction:

NaClO3 + NH4NO3 -) NaNO3 + NH4ClO3⇓



Experimental:

1- A boiling hot solution of 7.7g of NaClO3 and 13g of NH4NO3 in 12.5ml of H2O was made.

2-The solution was chilled to -3 degree Celsius and filtered.

3-Crystals were dried in a dark room for 1hour at RT and stored outside at -5 to -20 degree Celsius for future use ( Do not keep the product more than 3 days).


Yield: 6.57g


Crystal were tested by heating 0.1g on a steel blade with a methanol lamp. The NH4ClO3 leave almost no residue and smell chlorine. Flame test : it color the flame yellow, it seem to have some sodium ion. For the last test I added 0.1g of the salt on a plastic spoon and ligthed the spoon , were was the chlorate the spoon burned very fast, not like NH4NO3.

Conclusion:
NH4ClO3 made by this process need to be recrystalised with alcohol to get get rid of the sodium contamination. Adding ammonium carbonate could realy help to make the product less prone to rapid decomposition.



Reference:

For most of the solubility data:

en.Wikipedia.org

For general proprety of ammonium chlorate:

brauer, handbook of preparative inorganic chemistry

For the idea of the sythesis/process:

My own work




Picture will be added in a few days.

If someone can help me to correct this post it would be greatly appreciated.

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zoombafu - 24-2-2012 at 15:39

Good job. My only ideas are for you to add more information. Write up and abstract and introduction that is an overview on the theory of the synthesis. Also write a conclusion that shows what you learned, and how the experiment backs up your intro/abstract.

bbartlog - 24-2-2012 at 15:52

I think you would need to do a little more work (pictures, spellcheck, references) yourself before getting very much advice. But to start with:

- if this approach is based on something you read somewhere, include that reference. If it's something you came up with, at least include the solubility data that led you to conclude that this was likely to work.
- you contradict yourself. First you say you want to mix ammonium chlorate and calcium hydroxide, then you give an experimental where you mix ammonium nitrate and sodium chlorate. Is the former intended as a second step?
- there are ten or more typos/spelling errors in your short post. Some minor grammar errors due to English being a second language are one thing but there are automatic spell checkers that can fix things like 'aded','Unknow','electrolisis' etc.
- Even if you write it up properly with pictures, references and so on, a metathesis like this is sort of elementary. I hate to discourage contributions but it's pretty simple.

plante1999 - 24-2-2012 at 16:42

I corrected some mistakes and added more text. I'm making an conclusion.

AndersHoveland - 24-2-2012 at 17:00

Probably not a good idea to store it. The chemical degredation of ammonium chlorate over time could potentially lead to spontaneous detonation.

bbartlog - 24-2-2012 at 17:49

Nice improvements and glad you added some detail on the overall utility of the reaction. I would suggest calculating the percentage of theoretical yield that your fractional crystallization gives and adding that to the writeup.

plante1999 - 24-2-2012 at 18:09

I'm planning to recrystallise the NH4ClO3 with 99% Isopropanol to get rid of the sodium contamination, I will calculate the percentage of theoretical yield after.

Hexavalent - 25-2-2012 at 03:37

Good work, as aforementioned you will need to give references, an abstract and a conclusion. The only think I'd like to suggest is that you also include molar amounts of your reagents as well as gram amounts, as well as your percent yield, based on whatever reagent is your limiter (the chemical that is not in excess). If you're not sure on how to do these calculations, then revise the formula triange relating mass, molarity and Mr.

Pulverulescent - 25-2-2012 at 04:14

Ammonium chlorate has a well-deserved bad reputation!
But you can get barium chlorate here if you act promptly.

P

Formatik - 26-2-2012 at 16:01

I think probably the likely reason ammonium chlorate explodes spontaneously is because it degenerates, as it does evolving acidic gases. These acid generating gases (like Cl2) act on the chlorate. Na2CO3 or CaCO3 significantly increases stability of the chlorate, but it's hard to get a good homogenous mixture with powders, I wouldn't store it regardless. Acids or moisture increase its decomposition and even traces of acids cause decomposition of the pure compound.

When the solid has been spread out it tends to not explode, so it's best not to aggregate the powder as a mass or a pile and handle it as thin spread out layers. Solutions of it which have been stored have exploded after a few weeks, or just after having been boiled in reflux have exploded.

I would not store it and look out for signs of decomposition like yellow color, and check the pH it should be held neutral or slightly alkaline when it is made.

The shock sensitivity of the chlorate was determined by Kast with 2kg weight giving a 20cm drop height (which is 4Nm, about 1.6 times less impact sensitive than lead azide). Friction sensitivity is fairly high (the source for all data is Gmelin).

Concerning:
Quote: Originally posted by plante1999  


That solubility data isn't right it's given in Gmelin as 28.7g NH4ClO3 in 100g H2O at 0 deg C.

plante1999 - 26-2-2012 at 16:14

Maybe The reference that I took was inacurrate... In fact I have used almost all the chlorate today, I tested the chlorate, the pH was slightly alkaline. I will made another diagram soon.

Rosco Bodine - 26-2-2012 at 16:32

If the ammonium chlorate is alcohol soluble the copper complex may be interesting, but caution would be indicated because the copper ammonium complex is reportedly an initiator. And how stable is the copper complex is unknown, it may be not much more stable, but probably some, if it would
be reported as a potentially useful initiator. Adding tetrammonium copper nitrate
or possibly just copper nitrate to an alcohol solution of the ammonium chlorate
may do the trick, possibly trying addition of ammonium carbonate or bubbling free ammonia through the mixture. Likewise a nickel, cobalt, or zinc derivative
could form as a complex with ammonia or amines. Betaine may also react with the ammonium chlorate to form a product.

plante1999 - 26-2-2012 at 17:13

Quote: Originally posted by Rosco Bodine  
If the ammonium chlorate is alcohol soluble the copper complex may be interesting, but caution would be indicated because the copper ammonium complex is reportedly an initiator. And how stable is the copper complex is unknown, it may be not much more stable, but probably some, if it would
be reported as a potentially useful initiator. Adding tetrammonium copper nitrate
or possibly just copper nitrate to an alcohol solution of the ammonium chlorate
may do the trick, possibly trying addition of ammonium carbonate or bubbling free ammonia through the mixture. Likewise a nickel, cobalt, or zinc derivative
could form as a complex with ammonia or amines. Betaine may also react with the ammonium chlorate to form a product.


Ammonium Chlorate is alcohol solube, Complexing it would be really interessing. I hop someone would try my synthesis and give is opinion.

[Edited on 27-2-2012 by plante1999]

Formatik - 29-2-2012 at 23:30

Also using a hot solution might not be a good idea because ammonium chlorate is thermally unstable and solutions decompose (e.g. a literature value given in Gmelin is at around 75 C), in that regard it is similar to ammonium nitrite, but ammonium nitrite when decomposed in solution has been used to make nitrogen gas and does not carry the explosion risk with it since it decomposes to nitrogen and not other compounds like NCl3, etc.

plante1999 - 5-3-2012 at 12:18

I added a conclusion and reference.

From my own experiments ammonium chlorate is somewath stable in hot water(at least for 5 minute in boiling hot water) (it did not smell anything durring the process).

Hexavalent - 5-3-2012 at 12:48

I think I mentioned upthread, try to include mole equivalents of your gram quantities.

Nicodem - 5-3-2012 at 13:02

Quote: Originally posted by plante1999  
Experimental:

1- A boiling hot solution of 7.7g of NaClO3 and 13g of NH4NO3 in 12.5ml of H2O was made.

2-The solution was chilled to -3 degree Celsius and filtered.

3-Crystals were dried in a dark room for 1hour at RT and stored outside at -5 to -20 degree Celsius for future use ( Do not keep the product more than 3 days).


Yield: 6.57g

A properly written experimental part would be in order. There is no need to be lazy when it comes to properly describe experiments. Also, writing the experimental part in the classical format makes them more easy to read and follow (check an article from the field to see how it is done).
Quote:
NH4NO3, Ammonium nitrate 99%(approx) from high quality instant cold pack (5$ for 40g)

NaClO3, Sodium Chlorate 98-99%(approx) from electrolysis and recrystallised twice

How did you determine the assay (the above stated purity) of these reagents?
Quote:
Conclusion:
NH4ClO3 made by this process need to be recrystalised with alcohol to get get rid of the sodium contamination. Adding ammonium carbonate could realy help to make the product less prone to rapid decomposition.

Those are not conclusions. You confused hypotheses with conclusions. What is worrying is that you presented your hypotheses, which can potentially lead to unsafe situations such as explosions, as a proven fact (a conclusion based on experimental evidence). Is there a reference that says ammonium chlorate can be safely recrystallized from alcohols? If so, you need to provide it.

The solubility chart is misleading. You connected the discrete points with a line which causes it to present false data. Bar charts are commonly used for discrete points, or you can just put the unconnected points in an XY chart. You don't have enough points to connect them with a meaningful trend-line.

References to primary literature should be provided, especially for the factual data.

In the introduction you write several things that are not really connected to what you are presenting latter. There is nothing wrong to present your plans with the product, but you say almost nothing about the product and how it is made. Introductions generally provide a literature review on the topic in order to get the reader acquainted with the topic of the article.

There is a general lack of safety issues and caution warnings where there should be.

Hope this helps you to get a picture on how reports are written. If you will chose to become a chemist you will have to learn it anyway. Better sooner than later. Ask for specifics if I was too vague.

[Edited on 5/3/2012 by Nicodem]

plante1999 - 5-3-2012 at 13:15

Quote: Originally posted by Nicodem  


Is there a reference that says ammonium chlorate can be safely recrystallized from alcohols? If so, you need to provide it.



Yes, brauer handbook of preparative inorganic chemistry state that it could be made in an alcohol sol. with ammonium sulfate and a chlorate salt.

''How did you determine the assay (the above stated purity) of these reagents?''

For the Chlorate I tested with silver nitrate and it did not make a precipitate , the starting material for the electrolisis was of very good purity and after the electrolisis I recrystalised twice so I don't think there is much more than 1% impurity. I need to say that the nitrate salt here was tested with silver nitrate and it did not give a precipitate, I admit it COULD be only 97%. Maybe should I ad the process I use to determine the purity.

''A properly written experimental part would be in order. There is no need to be lazy when it comes to properly describe experiments. Also, writing the experimental part in the classical format makes them more easy to read and follow (check an article from the field to see how it is done).''

If someone send me a link to a properly written experimental I would change it.

''The solubility chart is misleading. You connected the discrete points with a line which causes it to present false data. Bar charts are commonly used for discrete points, or you can just put the unconnected points in an XY chart. You don't have enough points to connect them with a meaningful trend-line.''

You have a good point, I will change this.

In the introduction you write several things that are not really connected to what you are presenting latter. There is nothing wrong to present your plans with the product, but you say almost nothing about the product and how it is made. Introductions generally provide a literature review on the topic in order to get the reader acquainted with the topic of the article.

There is a general lack of safety issues and caution warnings where there should be.

Hope this helps you to get a picture on how reports are written. If you will chose to become a chemist you will have to learn it anyway. Better sooner than later. Ask for specifics if I was too vague.

I will change all these thing, I know I don't realy know how to do a report, I was my first attemp. I want to become a inorganic chemist and I know I need to learn convention. This is wy I need help.

Thank you

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Lithium - 6-5-2012 at 00:35

why don't you just add ammonium bitartrate to a boiling hot solution of KClO3? let the solution cool and filter through glass wool to obtain NH4ClO3 solution.

or, if HClO3 is desired, add tartaric acid to boiling KClO3 solution, cool to 10 degrees celsius and filter of potassium bitartrate.

seems much less problematic, IMO

Li

perhaps an improved method

virgilius1979 - 21-6-2012 at 10:50

I was also curious about synthesizing ammonium chlorate so I reacted (NH4)2SO4 with NaClO3 in water solution. I than added an equal volume of ethanol 96% that determined the immediate precipitation of Na2SO4. I filtered it, and kept the solution of NH4ClO3 and let the water evaporate under gentle heating (50 degrees C), than put to fridge to cool and precipitate and filtered the salt.
I let it dry on filter paper that put it on a glass plate and let it stay in low light. I must say it's very warm here, it's a hot summer and the temp. inside reaches 30C; still I didn't notice any visible signs of decomposition, like changing color, but there's a faint chlorine odor.
The filter paper which was impregnated with amm. chlorate burned vigorously with lots of smoke and chlorine.

Later edit: After a few days the chlorine smell became obvious in the room and I decided to get rid of it. Definitely not something to keep for long !

[Edited on 1-7-2012 by virgilius1979]