Metathesis reaction does not work for me

[THEONE]

I have tried to make some kclo3 with naclo3-kno3 and one more time with 66%-33% kcl-nacl. I have failed both of times. I have dissolve the correct amount of salts and mix them together. I end up both of times with few grams of naclo3!! LOL No kclo3 at all

[WSM]

I have tried to make some kclo3 with naclo3-kno3 and one more time with 66%-33% kcl-nacl. I have failed both of times. I have dissolve the correct amount of salts and mix them together. I end up both of times with few grams of naclo3!! LOL No kclo3 at all

 

I wonder, if you electrolyse the potassium/sodium chlorides mix (in solution), whether it would selectively drop out the potassium chlorate as it forms?

 

Do you have MMO and titanium electrodes? That would be the first place to start.

 

If you're up to doing the experiment, we can offer suggestions that may assist you in avoiding problems and pitfalls along the way. Let us know.

 

WSM

[THEONE]

Mno2 homemade anode and SS 316 cathode. The naclo3 is quite pure as i checked it with sugar mix. Kno3 is fertilizer grade but pure enough also. The 66-33 kcl-nacl is for salt substitude, high purity.

[THEONE]

WSN in the furute i want to make some ammonium perchlorate, so i need to work well the metathesis reaction

[WSM]

WSN in the furute i want to make some ammonium perchlorate, so i need to work well the metathesis reaction

 

If you have a good grade of NaClO₃ and either a platinum or LD anode, making NaClO₄ should be no problem. From there, making other perchlorates is a matter of careful attention to detail and good lab practices. I haven't tried to make the ammonium salt but just the potassium salt, and so far it's been a success.

 

Making ammonium perchlorate similar to the commercial grades involves a LOT more handling than I care to attempt. Making potassium perchlorate in pyrotechnic grades is the limit of my ambitions. So many excellent pyrotechnic compositions can be made with KClO₄ that I'm satisfied with that level of achievement. That may change in the future, but for now that's as far as I wish to go.

 

WSM

[WSM]

Mno2 homemade anode and SS 316 cathode. The naclo3 is quite pure as i checked it with sugar mix. Kno3 is fertilizer grade but pure enough also. The 66-33 kcl-nacl is for salt substitude, high purity.

 

Again, I suspect an electrolyte solution of just the salt substitute (2:1, KCl:NaCl) in an active chlorate cell would selectively drop out KClO₃ as it runs due to the lower solubility of that salt in relation to the other ionic species in the electrolyte. After the initial run, recharging the depleted electrolyte with more salt substitute should encourage a greater yield more quickly than the initial run of the chlorate cell.

 

Due to the solubilities involved, I think it'll work. If you try it, let us know how it works.

 

WSM

[schroedinger]

Yes WSM that is what happens

 

@WSM how long did you wait for the KClO3 to form? It can take quite aome time for the KClO3 to precipate.

Also how much NaClO4 did you use in what volume?

[WSM]

Yes WSM that is what happens

 

@WSM how long did you wait for the KClO3 to form? It can take quite aome time for the KClO3 to precipate.

Also how much NaClO4 did you use in what volume?

 

For the initial run, I notice the KClO₃ crystals forming near the end of the run, but I'm using KCl water softener salt (not salt substitute). With subsequent runs, recharged with more KCl, the KClO₃ crystals start to form right away and drop like snowflakes in the mother liquor, to the bottom of the cell.

 

So far, I'm using 100 ml samples of my NaClO₄ solution (cell liquor), right from the cell. After destroying the residual chlorate, I add concentrated, room temperature KCl solution and the KClO₄ drops out instantly. Next I've been vacuum filtering the perchlorate out and rinsing it with cold distilled water. Next, I dry the crystals (fine white powder, actually) in an evaporation dish over boiling water.

 

My plan is to determine if my process makes "pyro ready" perchlorate. If the answer is yes, then process all the rest of the sodium perchlorate to potassium perchlorate and document it. If no, continue the purification process till it does, and process the remainder of the sodium perchlorate as above.

 

I hope that answers your questions. If not, re-word them and ask again. Thanks.

 

WSM

[Mumbles]

My experiences are much like that of WSM's. I've never experienced KClO3 or KClO4 exhibit any hesitation in precipitating. You do need to use cold water, or chill the solution to get maximum yield though. Potassium chlorate is about 3x as soluble at room temperature as at 0C. Remember that the solubility of KClO3 at 0C is 3g/100mL, and around 8 or 9g/100mL at room temperature. There is inherent loss always in this process. If you are going too dilute or trying to process too little at once you'll get poor to no yield. This also manifests itself in the first run from a chlorate cell giving poorer yield than the subsequent runs.

 

THEONE, I'm still not entirely convinced you're making as much chlorate as you think. Calling it pure, and getting something flammable is poor proof it actually is what you think it is. It doesn't take all that much sodium chlorate mixed with salt to render a flammable mixture with sugar. Since you're using unproven homemade electrodes, this is where I'd look first. If you can, you might want to try a spot test to see how much chloride remains in your sample.

[THEONE]

Mumbles how do you explain the fact that Naclo3 ppt out ?

[Mumbles]

Well, mostly I'm not confident you actually are getting NaClO3 out. Given your questionable positive identification of it out of your cell, how do you expect to have any better identification of it after precipitation?

[Arthur]

Also do remember that metathesis is quoted using KCl but you try using KNO3. I can see why but don't have the thermodynamic tables to check whether it will work. Also once you put nitrate in there the solution may not recycle.

[THEONE]

Arthur that is true. I tried kno3 because i can not find kcl. If you can check if kno3 is working it would be useful. Edited September 22, 2015 by THEONE

[schroedinger]

KNO3 is working and will leave you with NaNO3.

 

One thing that i don't understand, how do you get NaClO3 to precipate? It has a solubility of 805 g/L @0ºC and 988 g/L 20ºC.

 

Sodium Nitrate has 70,07 g/L @ 0ºC ang 808 @20ºC.

 

Pottasium nitrate has 133 @ 0 and 317 @ 20.

 

If you compare these numbers, and say no reaction occurs and you mix them @20ºC and chill to 0ºC you will find that only pottasium nitrate should precipate with some trace ammount of the Sodium Chlorate and a little bit of Sosium Nitrate.

 

But it is easy to test if you have K or Na Chlorate.

Take a 50 g sample an0of your salt and put it into 100 ml of boiling distilled Water. After everything is dissolved let it cool to roomtemperature. If something precipates you have KClO3 ( should be about 40 g).

KNO3 is working and will leave you with NaNO3.

 

One thing that i don't understand, how do you get NaClO3 to precipate? It has a solubility of 805 g/L @0ºC and 988 g/L 20ºC.

 

Sodium Nitrate has 70,07 g/L @ 0ºC ang 808 @20ºC.

 

Pottasium nitrate has 133 @ 0 and 317 @ 20.

 

If you compare these numbers, and say no reaction occurs and you mix them @20ºC and chill to 0ºC you will find that only pottasium nitrate should precipate with some trace ammount of the Sodium Chlorate and a little bit of Sosium Nitrate.

 

But it is easy to test if you have K or Na Chlorate.

Take a 50 g sample an0of your salt and put it into 100 ml of boiling distilled Water. After everything is dissolved let it cool to roomtemperature. If something precipates you have KClO3 ( should be about 40 g).

KNO3 is working and will leave you with NaNO3.

 

One thing that i don't understand, how do you get NaClO3 to precipate? It has a solubility of 805 g/L @0ºC and 988 g/L 20ºC.

 

Sodium Nitrate has 70,07 g/L @ 0ºC ang 808 @20ºC.

 

Pottasium nitrate has 133 @ 0 and 317 @ 20.

 

If you compare these numbers, and say no reaction occurs and you mix them @20ºC and chill to 0ºC you will find that only pottasium nitrate should precipate with some trace ammount of the Sodium Chlorate and a little bit of Sosium Nitrate.

 

But it is easy to test if you have K or Na Chlorate.

Take a 50 g sample an0of your salt and put it into 100 ml of boiling distilled Water. After everything is dissolved let it cool to roomtemperature. If something precipates you have KClO3 ( should be about 40 g).

KNO3 is working and will leave you with NaNO3.

 

One thing that i don't understand, how do you get NaClO3 to precipate? It has a solubility of 805 g/L @0ºC and 988 g/L 20ºC.

È

Sodium Nitrate has 70,07 g/L @ 0ºC ang 808 @20ºC.

 

Pottasium nitrate has 133 @ 0 and 317 @ 20.

 

If you compare these numbers, and say no reaction occurs and you mix them @20ºC and chill to 0ºC you will find that only pottasium nitrate should precipate with some trace ammount of the Sodium Chlorate and a little bit of Sosium Nitrate.

 

But it is easy to test if you have K or Na Chlorate.

Take a 50 g sample an0of your salt and put it into 100 ml of boiling distilled Water. After everything is dissolved let it cool to roomtemperature. If something precipates you have KClO3 ( should be about 40 g).

[WSM]

KNO3 is working and will leave you with NaNO3.

One thing that i don't understand, how do you get NaClO3 to precipate? It has a solubility of 805 g/L @0ºC and 988 g/L 20ºC.

Sodium Nitrate has 70,07 g/L @ 0ºC ang 808 @20ºC.

Pottasium nitrate has 133 @ 0 and 317 @ 20.

If you compare these numbers, and say no reaction occurs and you mix them @20ºC and chill to 0ºC you will find that only pottasium nitrate should precipate with some trace ammount of the Sodium Chlorate and a little bit of Sosium Nitrate.

But it is easy to test if you have K or Na Chlorate.

Take a 50 g sample an0of your salt and put it into 100 ml of boiling distilled Water. After everything is dissolved let it cool to roomtemperature. If something precipates you have KClO3 ( should be about 40 g).

KNO3 is working and will leave you with NaNO3.

 

I believe you need to make the temperatures and solubilities work for you.

 

Since sodium chlorate is the most soluble component in the mix, remove the less soluble parts (by temperature control and relative solubilities) till you're left with (relatively) pure sodium chlorate, then concentrate the sodium chlorate solution (boil the water off) till the sodium chlorate starts to crystallize out.

 

WSM

[pyrojig]

I love the thinking backwards method .I agree that using solubility's in your favor is the key. I fought this for the longest time , but have a very diff. view after watching some of the work shown here. There are other methods to test for chlorates as well. One that comes to mind is the sugar/ chlorate + sulfuric acid test. It should light up pretty quick with this method in the sun shine. ( if chlorate is present. ) Perch doesnt do this reaction . Chloric acid is way more reactive than perchloric acid. Merk index is a gold mine for testing reagents as well.

 

 

Mno2 homemade anode and SS 316 cathode. The naclo3 is quite pure as i checked it with sugar mix. Kno3 is fertilizer grade but pure enough also. The 66-33 kcl-nacl is for salt substitude, high purity.

Edited September 27, 2015 by pyrojig

[WSM]

I love the thinking backwards method .I agree that using solubility's in your favor is the key. I fought this for the longest time , but have a very diff. view after watching some of the work shown here. There are other methods to test for chlorates as well. One that comes to mind is the sugar/ chlorate + sulfuric acid test. It should light up pretty quick with this method in the sun shine. ( if chlorate is present. ) Perch doesnt do this reaction . Chloric acid is way more reactive than perchloric acid. Merk index is a gold mine for testing reagents as well.

 

Testing for chlorate by mixing chlorate plus a fuel and testing with sulfuric acid isn't foolproof.

 

Some chlorate containing compositions won't always ignite (smoke compositions including sodium bicarbonate, for example) and some compositions not containing chlorate can ignite when sulfuric acid is added, giving a false positive for chlorate.

 

There are three chemical spot test reagents for chlorate that I've used (and they all work):

1. aniline hydrochloride
2. indigo carmine
3. N-phenylanthranilic acid

In my sodium perchlorate purification process (before conversion to potassium perchlorate) I tested for residual chlorate first with the indigo carmine reagent. That test failed. It gave false positives because of the sulfates present in the solution; left over from the metabisulfite use.

 

I switched to testing with N-phenylanthranilic acid (or NPAA as Swede used to call it), and it worked without problems. Once I quit getting positive indications for chlorate, I added potassium chloride solution to the (now chlorate-free) sodium perchlorate solution and it immediately dropped out the fine white solid potassium perchlorate crystals (powder, actually).

 

After filtering and rinsing with cold distilled water in a vacuum filtration set up, I dried and stored the fresh potassium perchlorate sample for later testing.

 

WSM

Edited October 10, 2015 by WSM

[pyrojig]

WSM ; you do make a good point , I was pointing out for the simple mix of chlorate and sugar, this works pretty well, but as you said , testing for other fuel mixtures can pose a problem . ( which I didnt consider at the time of posting ). I appreciate the correction , and good points made/ . Is the NPAA something that can be obtained with out a legit (business license ) purchase ?

Edited October 14, 2015 by pyrojig

[WSM]

WSM ; you do make a good point , I was pointing out for the simple mix of chlorate and sugar, this works pretty well, but as you said , testing for other fuel mixtures can pose a problem . ( which I didnt consider at the time of posting ). I appreciate the correction , and good points made/ . Is the NPAA something that can be obtained with out a legit (business license ) purchase ?

 

A very good question, to which I'm inclined to say no. It seems to be very hard to get. I think chemical companies are avoiding selling material to individuals (or anyone who's pockets aren't deeper than theirs) to minimize their liability. I don't blame them, but it sure gets in the way of my research and progress.

 

When Swede showed the use of NPAA in his blogs, I looked high and low for some and after an exhaustive search (and not just a few doors slammed in my face) I was able to convince a friend in industry that my intentions were honorable and he allowed me to buy some. I shared a sample of it with Swede and he was surprised it was higher quality than the material he was using.

 

NPAA wasn't my first choice for detection of chlorate (ClO₃^-) in solution, but it has worked the best, so far, in my perchlorate research. I plan to stick with it.

 

WSM

Edited October 14, 2015 by WSM

[WSM]

A very good question, to which I'm inclined to say no. It seems to be very hard to get. I think chemical companies are avoiding selling material to individuals (or anyone who's pockets aren't deeper than theirs) to minimize their liability. I don't blame them, but it sure gets in the way of my research and progress.

When Swede showed the use of NPAA in his blogs, I looked high and low for some and after an exhaustive search (and not just a few doors slammed in my face) I was able to convince a friend in industry that my intentions were honorable and he allowed me to buy some. I shared a sample of it with Swede and he was surprised it was higher quality than the material he was using.

NPAA wasn't my first choice for detection of chlorate (ClO₃^-) in solution, but it has worked the best, so far, in my perchlorate research. I plan to stick with it.

WSM

 

I did a search on eBay and found NPAA available, 25 g for $35 delivered! It's from Eastern Europe and includes free shipping to the US. I ordered a bottle and we'll see what comes (and when).

 

If this proves to be a good source, it'll be a boon to electro-chemists and others who wish to test for chlorates.

 

WSM

[WSM]

 

I wonder, if you electrolyse the potassium/sodium chlorides mix (in solution), whether it would selectively drop out the potassium chlorate as it forms?

 

Do you have MMO and titanium electrodes? That would be the first place to start.

 

If you're up to doing the experiment, we can offer suggestions that may assist you in avoiding problems and pitfalls along the way. Let us know.

 

WSM

 

For those who don't have access to potassium chloride, but do have access to the salt substitute (sodium and potassium chlorides mixed); have you ever tried running (a solution of) it in a chlorate cell using MMO and titanium electrodes?

 

If so, how did it work? I'm curious to know if my guess is correct, will the potassium chlorate selectively drop out as it's formed? Please let us know. Thanks.

 

WSM

Edited January 1, 2016 by WSM

[Sulphurstan]

Instead of starting a new topic, I put my question here: did anyone ever tried to produce AP from a NaClO4 solution, then pouring NH4Cl in, instead of the classical KCl?

Since both the resulting products AP and NaCl are soluble, could there be a way to precipitate only the AP?

This is the method given in fast by T Shimizu, I must be misunderstanding something here....

 

Mixing NH4OH and HClO4 would do, but no access to this acid....

[WSM]

Instead of starting a new topic, I put my question here: did anyone ever tried to produce AP from a NaClO4 solution, then pouring NH4Cl in, instead of the classical KCl?

Since both the resulting products AP and NaCl are soluble, could there be a way to precipitate only the AP?

This is the method given in fast by T Shimizu, I must be misunderstanding something here....

Mixing NH4OH and HClO4 would do, but no access to this acid....

 

There must be, because that's the way industry does it. I suppose they're separated by selective crystallizing one out before the other.

 

If you study the solubilities (try Google), you may see how it can be done..

 

WSM

[Mumbles]

I think this metathesis primarily operates on the principle that sodium perchlorate is much more soluble than anything else. This can help to cut the losses. At 0C, ammonium perchlorate is about 1/3 as soluble as sodium chloride so it will preferentially precipitate. I'm sure the devil is in the details though, as in how much and what concentration of each to optimally drive this metathesis. Let us know what you discover if you try it out.

 

My inclination would be to start with a stoichiometric ratio with volumes and concentrations to give about a 80-90% of saturated NaCl solution at the end. 300-330g/L of NaCl. Salt mixtures behave oddly, as ionic strength can further crash certain materials out.

 

Maybe industrial ratios or procedures could be found too.

[Sulphurstan]

Mumbles. Thanx for these advices. Ill purchase some na clo4 with my next order of chems, and make some tries...