megalomania
May 18th, 2003, 03:41 PM
Bitter
Frequent Poster
Posts: 290
From: 11 Downing Street, London, England
Registered: SEP 2000
posted 03-30-2001 03:40 PM
--------------------------------------------------------------------------------
I am sure many of you are aware, it is possible to change sodium chlorate to potassium chlorate by mixing it with KCl. The potassium chlorate can be extracted because it is considerably less soluble in water than the sodium chloride by-product.
Well how about this : Because ammonium perchlorate is so difficult to acquire outside the US, then I was thinking could it be made using a similar method to the one above from potassium perchlorate by mixing it with ammonium nitrate.
I looked up some sources and I found that it would probably work :
0 deg C 100 deg C
NH4ClO4 10.74 42.45
KClO4 0.75 21.8
NH4NO3 118.3 871
KNO3 13.3 247
The numbers are the solubility (in grams) per 100cc of water.
Therefore, if 80g of ammonium nitrate was dissolved in 100g of boiling water and 138g of pure potassium perchlorate was added, about 75g of ammonium perchlorate would, in theory, be precipitated. The hot water would immediately have to be tipped away (otherwise KNO3 might be precipitated along with the perchlorate).
The only problem I can see with this is the danger of potassium chorate being present in the perchlorate, which would reduce the possibility of safely using home-made perchlorate to zero.
Any opinions ?
Anthony
Moderator
Posts: 2306
From: England
Registered: SEP 2000
posted 03-30-2001 06:15 PM
--------------------------------------------------------------------------------
My first reaction was ammonium chlorate... Then I realised that you were using KCLO4 instead of NaCLO3 and I thought that might be a waste of perfectly good KCLO4.
I agree, there is a risk of NH4CLO3 of forming as there's bound to be some KCLO3 in the KCLO4.
Is NH4CLO4 really so great though? I understand that it gives better performance in rocket fuels than KCLO4 due to all the combustion products being gases, but it sounds like hard work. If you're doing rocket fuels, have you considered NH4NO3? IIRC it's got about half the performance of NH4CLO4 but its rediculously cheap and doesn't require the work that NH4CLO4 takes to make. You could always just make bigger motors to overcome the power loss. It's soemthing I intend to experiment with when the wheather gets a bit better.
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
Registered: MAR 2001
posted 03-30-2001 06:25 PM
--------------------------------------------------------------------------------
If your using rocket fuels you wouldnt want AN would you? As far as I understand it can detonate at high temperatures...??
firebreether
Frequent Poster
Posts: 110
From:
Registered: NOV 2000
posted 03-30-2001 09:16 PM
--------------------------------------------------------------------------------
no it DEFINITELY won't detonate. AN burns at lower temps than perchlorate, so it wouldn't be as good. Not to mention its super hygroscopic.
Anthony
Moderator
Posts: 2306
From: England
Registered: SEP 2000
posted 03-31-2001 08:56 AM
--------------------------------------------------------------------------------
I would think that NH4CLO4 is also very hygroscopic. If you using a plastic fuel/binder then it shouldn't be as much of a problem. Also have a "blast plug" (recommended) would make the motor 100% water/air tight.
The main point is AN is veeeeeery cheap.
Bitter
Frequent Poster
Posts: 290
From: 11 Downing Street, London, England
Registered: SEP 2000
posted 03-31-2001 01:32 PM
--------------------------------------------------------------------------------
I think you sould compare the figures I have given above to compare the water solubility (and to some extent hygroscopicy) of the chemical. NH4ClO4 is lower than KNO3 and about 10 times lower than NH4NO3
Anthony
Moderator
Posts: 2306
From: England
Registered: SEP 2000
posted 03-31-2001 03:06 PM
--------------------------------------------------------------------------------
I should have been more specific, I meant that NH4CLO4 would be very hygroscopic compared to the original KCLO4.
Agent Blak
Frequent Poster
Posts: 766
From: Sk. Canada
Registered: SEP 2000
posted 04-02-2001 10:00 AM
--------------------------------------------------------------------------------
If we are going to use Chemistry short hand when dealing with chemicals please do it right ; that way everyone know what each other means.
ie. Potassium Chlorate is KClO3 not KCLO3; Potassium PerChlorate is KClO4 not KCLO4... and so on and so forth.
This should help clear up some misunderstandings between members.
------------------
A wise man once said:
"...There Will Be No
Stand Off At High Noon
... Shoot'em In The Back
And, Shoot'em In The Dark"
Agent Blak-------OUT!!
firebreether
Frequent Poster
Posts: 110
From:
Registered: NOV 2000
posted 04-02-2001 09:56 PM
--------------------------------------------------------------------------------
All nitrates are verysoluble and hygroscopic. I thought chlorates and perchlorates could be for the NH4 and Na and Li forms. But the K forms are not which is good.
firebreether
Frequent Poster
Posts: 110
From:
Registered: NOV 2000
posted 04-03-2001 09:30 PM
--------------------------------------------------------------------------------
Also, because KClO4 is barely soluble, and NH4ClO4 is soluble, you won't ever get NH4ClO4 to precipitate from KClO4.
PHILOU Zrealone
Frequent Poster
Posts: 479
From: Brussels,Belgium,Europe
Registered: SEP 2000
posted 04-05-2001 05:04 AM
--------------------------------------------------------------------------------
100% right firebreether!
BTW: here are processes to make HClO4 and NH4ClO4
For the Newbies: NH4ClO4 can't be made by electrolyse of NH4Cl because you go through the dangerous NH4ClO3(VOD=3300m/s, spontaneously, unpredictably, self detonating even in solution)!!!!
1)Use CaCl2 (or Ca(ClO)2) and electrolyse it the same way you would do to get KClO3 or NaClO3 from NaCl and KCl.Yes CaCl2 is not very soluble but it is good so believe me!
You will of course get some Ca(ClO4)2 aside with Ca(ClO3)2.
Concentrate by evaporation and add diluted H2SO4 - or what is the same add conc. H2SO4 to the diluted mother liquor. (DON'T ADD CONC H2SO4 TO A CONCENTRATE SOLUTION OF CHLORATE/PERCHLORATE!!!!! BECAUSE HCLO3 AND HCLO4 ARE EXPLOSIVE WHEN CONCENTRATE!!!!!).
White clouds of unsoluble CaSO4 (plaster) will form and precipitate.Add until no more precipitate form while taking some of the clear solution and testing it with H2SO4).
CaCl2+O+heat+electricity--> Ca(ClO)2+ Ca(ClO2)2 +Ca(ClO3)2 + Ca(ClO4)2
The more the time of reaction the more you go to Ca(ClO4)2!!!!
Ca(ClO4)2 + Ca(ClO3)2 + 2 H2SO4--> 2CaSO4 + 2HClO4 + 2HClO3
Filter the plaster through glass paper filter (used to cover walls before paint application to avoid irregularities-glass doesn't react with oxydising acid like perchloric and chloric what paper does!).
Now we have a diluted to medium concentration solution of HClO3 and HClO4 in water.
To get rid of the HClO3 for further process boil the solution by slowly increasing the heat in a wel ventilated area avoiding going over 150C.
By the magic of chemistry:
4HClO3(diluted)+heat--> 3HClO4 + HCl
(this reaction looks pretty the same as
4NaClO3 + heat (not too much)--> 3NaClO4 + NaCl
did you notice that?)
Anyway,upon slow boiling HCl is driven away (reason why it has to be done outside otherwise all metals and your lungs will be corroded); So does water.
You end with a solution stil concentrating in HClO4 by evaporation of the water.
Since HClO4 has an eutectic with 79%HClO4/21%H2O at approx 180C and that it becomes explosive when more concentrate, stop at 150C, no use to loose the valuable HClO4.
Now simply mix concentrate NH3 (in excess) solution with the HClO4 solution to get NH4ClO4. Evaporate in the open excess NH3 will go away. You get your NH4ClO4 from not to expensive starting materials.
BTW: DON'T USE a pan to boil the mix since METALS AND ACID ARE NOT GOOD FRIENDS always use pyrex glassware.Also to know HCLO4 is catalyticly decomposed by metals when very concentrate over 79%, it explodes aslo upon contact with alcools (and cellulose is a polyalcool) making the dangerous organic perchloric esters.
2)Even less expensive:
Mix under stiring sodium chlorate with concentrate HCl in excess (you can only reach max 37% HCl)and heat gently until it dissolves. cool down NaCl cristallises out (solubility of NaCl is 30g/100g H2O); filter out and keep the 37% HClO3 solution.
NaClO3 + conc HCl < == > HClO3 + NaCl
Boil the HClO3 slowly in an open space following the same reaction as in the first process:
4HClO3 + heat --> 3HClO4 + HCl
HCl is more volatile and fky away.
Go to 150C.
THen when cool add some excess NH3 solution.
HClO4 + NH4OH --> NH4ClO4 + H2O
------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"
Bitter
Frequent Poster
Posts: 290
From: 11 Downing Street, London, England
Registered: SEP 2000
posted 04-05-2001 09:52 AM
--------------------------------------------------------------------------------
I was well aware of the insolubility of the KClO4, but I was hoping it would gradually dissolve and turn to AmPer slowly.
I'll post the perchloric acid method shortly (that's using hypochlorite, not the ones posted by Philou ), I think you'll find that works much better. But first I'll experiment to see if this homemade perchloric acid of mine is sucessful as the commercial stuff.
So far, I have only tried it with 60% commercial perchloric acid.
Frequent Poster
Posts: 290
From: 11 Downing Street, London, England
Registered: SEP 2000
posted 03-30-2001 03:40 PM
--------------------------------------------------------------------------------
I am sure many of you are aware, it is possible to change sodium chlorate to potassium chlorate by mixing it with KCl. The potassium chlorate can be extracted because it is considerably less soluble in water than the sodium chloride by-product.
Well how about this : Because ammonium perchlorate is so difficult to acquire outside the US, then I was thinking could it be made using a similar method to the one above from potassium perchlorate by mixing it with ammonium nitrate.
I looked up some sources and I found that it would probably work :
0 deg C 100 deg C
NH4ClO4 10.74 42.45
KClO4 0.75 21.8
NH4NO3 118.3 871
KNO3 13.3 247
The numbers are the solubility (in grams) per 100cc of water.
Therefore, if 80g of ammonium nitrate was dissolved in 100g of boiling water and 138g of pure potassium perchlorate was added, about 75g of ammonium perchlorate would, in theory, be precipitated. The hot water would immediately have to be tipped away (otherwise KNO3 might be precipitated along with the perchlorate).
The only problem I can see with this is the danger of potassium chorate being present in the perchlorate, which would reduce the possibility of safely using home-made perchlorate to zero.
Any opinions ?
Anthony
Moderator
Posts: 2306
From: England
Registered: SEP 2000
posted 03-30-2001 06:15 PM
--------------------------------------------------------------------------------
My first reaction was ammonium chlorate... Then I realised that you were using KCLO4 instead of NaCLO3 and I thought that might be a waste of perfectly good KCLO4.
I agree, there is a risk of NH4CLO3 of forming as there's bound to be some KCLO3 in the KCLO4.
Is NH4CLO4 really so great though? I understand that it gives better performance in rocket fuels than KCLO4 due to all the combustion products being gases, but it sounds like hard work. If you're doing rocket fuels, have you considered NH4NO3? IIRC it's got about half the performance of NH4CLO4 but its rediculously cheap and doesn't require the work that NH4CLO4 takes to make. You could always just make bigger motors to overcome the power loss. It's soemthing I intend to experiment with when the wheather gets a bit better.
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
Registered: MAR 2001
posted 03-30-2001 06:25 PM
--------------------------------------------------------------------------------
If your using rocket fuels you wouldnt want AN would you? As far as I understand it can detonate at high temperatures...??
firebreether
Frequent Poster
Posts: 110
From:
Registered: NOV 2000
posted 03-30-2001 09:16 PM
--------------------------------------------------------------------------------
no it DEFINITELY won't detonate. AN burns at lower temps than perchlorate, so it wouldn't be as good. Not to mention its super hygroscopic.
Anthony
Moderator
Posts: 2306
From: England
Registered: SEP 2000
posted 03-31-2001 08:56 AM
--------------------------------------------------------------------------------
I would think that NH4CLO4 is also very hygroscopic. If you using a plastic fuel/binder then it shouldn't be as much of a problem. Also have a "blast plug" (recommended) would make the motor 100% water/air tight.
The main point is AN is veeeeeery cheap.
Bitter
Frequent Poster
Posts: 290
From: 11 Downing Street, London, England
Registered: SEP 2000
posted 03-31-2001 01:32 PM
--------------------------------------------------------------------------------
I think you sould compare the figures I have given above to compare the water solubility (and to some extent hygroscopicy) of the chemical. NH4ClO4 is lower than KNO3 and about 10 times lower than NH4NO3
Anthony
Moderator
Posts: 2306
From: England
Registered: SEP 2000
posted 03-31-2001 03:06 PM
--------------------------------------------------------------------------------
I should have been more specific, I meant that NH4CLO4 would be very hygroscopic compared to the original KCLO4.
Agent Blak
Frequent Poster
Posts: 766
From: Sk. Canada
Registered: SEP 2000
posted 04-02-2001 10:00 AM
--------------------------------------------------------------------------------
If we are going to use Chemistry short hand when dealing with chemicals please do it right ; that way everyone know what each other means.
ie. Potassium Chlorate is KClO3 not KCLO3; Potassium PerChlorate is KClO4 not KCLO4... and so on and so forth.
This should help clear up some misunderstandings between members.
------------------
A wise man once said:
"...There Will Be No
Stand Off At High Noon
... Shoot'em In The Back
And, Shoot'em In The Dark"
Agent Blak-------OUT!!
firebreether
Frequent Poster
Posts: 110
From:
Registered: NOV 2000
posted 04-02-2001 09:56 PM
--------------------------------------------------------------------------------
All nitrates are verysoluble and hygroscopic. I thought chlorates and perchlorates could be for the NH4 and Na and Li forms. But the K forms are not which is good.
firebreether
Frequent Poster
Posts: 110
From:
Registered: NOV 2000
posted 04-03-2001 09:30 PM
--------------------------------------------------------------------------------
Also, because KClO4 is barely soluble, and NH4ClO4 is soluble, you won't ever get NH4ClO4 to precipitate from KClO4.
PHILOU Zrealone
Frequent Poster
Posts: 479
From: Brussels,Belgium,Europe
Registered: SEP 2000
posted 04-05-2001 05:04 AM
--------------------------------------------------------------------------------
100% right firebreether!
BTW: here are processes to make HClO4 and NH4ClO4
For the Newbies: NH4ClO4 can't be made by electrolyse of NH4Cl because you go through the dangerous NH4ClO3(VOD=3300m/s, spontaneously, unpredictably, self detonating even in solution)!!!!
1)Use CaCl2 (or Ca(ClO)2) and electrolyse it the same way you would do to get KClO3 or NaClO3 from NaCl and KCl.Yes CaCl2 is not very soluble but it is good so believe me!
You will of course get some Ca(ClO4)2 aside with Ca(ClO3)2.
Concentrate by evaporation and add diluted H2SO4 - or what is the same add conc. H2SO4 to the diluted mother liquor. (DON'T ADD CONC H2SO4 TO A CONCENTRATE SOLUTION OF CHLORATE/PERCHLORATE!!!!! BECAUSE HCLO3 AND HCLO4 ARE EXPLOSIVE WHEN CONCENTRATE!!!!!).
White clouds of unsoluble CaSO4 (plaster) will form and precipitate.Add until no more precipitate form while taking some of the clear solution and testing it with H2SO4).
CaCl2+O+heat+electricity--> Ca(ClO)2+ Ca(ClO2)2 +Ca(ClO3)2 + Ca(ClO4)2
The more the time of reaction the more you go to Ca(ClO4)2!!!!
Ca(ClO4)2 + Ca(ClO3)2 + 2 H2SO4--> 2CaSO4 + 2HClO4 + 2HClO3
Filter the plaster through glass paper filter (used to cover walls before paint application to avoid irregularities-glass doesn't react with oxydising acid like perchloric and chloric what paper does!).
Now we have a diluted to medium concentration solution of HClO3 and HClO4 in water.
To get rid of the HClO3 for further process boil the solution by slowly increasing the heat in a wel ventilated area avoiding going over 150C.
By the magic of chemistry:
4HClO3(diluted)+heat--> 3HClO4 + HCl
(this reaction looks pretty the same as
4NaClO3 + heat (not too much)--> 3NaClO4 + NaCl
did you notice that?)
Anyway,upon slow boiling HCl is driven away (reason why it has to be done outside otherwise all metals and your lungs will be corroded); So does water.
You end with a solution stil concentrating in HClO4 by evaporation of the water.
Since HClO4 has an eutectic with 79%HClO4/21%H2O at approx 180C and that it becomes explosive when more concentrate, stop at 150C, no use to loose the valuable HClO4.
Now simply mix concentrate NH3 (in excess) solution with the HClO4 solution to get NH4ClO4. Evaporate in the open excess NH3 will go away. You get your NH4ClO4 from not to expensive starting materials.
BTW: DON'T USE a pan to boil the mix since METALS AND ACID ARE NOT GOOD FRIENDS always use pyrex glassware.Also to know HCLO4 is catalyticly decomposed by metals when very concentrate over 79%, it explodes aslo upon contact with alcools (and cellulose is a polyalcool) making the dangerous organic perchloric esters.
2)Even less expensive:
Mix under stiring sodium chlorate with concentrate HCl in excess (you can only reach max 37% HCl)and heat gently until it dissolves. cool down NaCl cristallises out (solubility of NaCl is 30g/100g H2O); filter out and keep the 37% HClO3 solution.
NaClO3 + conc HCl < == > HClO3 + NaCl
Boil the HClO3 slowly in an open space following the same reaction as in the first process:
4HClO3 + heat --> 3HClO4 + HCl
HCl is more volatile and fky away.
Go to 150C.
THen when cool add some excess NH3 solution.
HClO4 + NH4OH --> NH4ClO4 + H2O
------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"
Bitter
Frequent Poster
Posts: 290
From: 11 Downing Street, London, England
Registered: SEP 2000
posted 04-05-2001 09:52 AM
--------------------------------------------------------------------------------
I was well aware of the insolubility of the KClO4, but I was hoping it would gradually dissolve and turn to AmPer slowly.
I'll post the perchloric acid method shortly (that's using hypochlorite, not the ones posted by Philou ), I think you'll find that works much better. But first I'll experiment to see if this homemade perchloric acid of mine is sucessful as the commercial stuff.
So far, I have only tried it with 60% commercial perchloric acid.