Sciencemadness Discussion Board

Potassium Chlorate & Perchlorate

NHZ - 10-8-2011 at 18:07

Hi all, I am new to this forum and been reading much recently but have not found anything really specific to my questions. I am making an electrolysis cell to produce small amounts of KCLO3 and would then like to convert that into KCLO4 as from what ive read, it is more stable and safer to handle.

I recently purchased some MMO coated titanium mesh and some glassware. I have the P/S and the materials to make the chlorate etc. so I think im covered in that regard.

I have no background in chemistry, so any advice offered would be greatly appreciated.

My first obstacle is finding a method of converting the chlorate and have found an interesting video on youtube as seen in this link > http://www.youtube.com/watch?v=9YVsEX-ikUQ

In the video it is said that the conversion can be performed using peroxide and alcohol. Does this appear to be correct? and is this procedure relatively safe?

I have seen a few other methods, but this one seems to be the simple route, though I am not sure how safe it is:(



Edit:

The video is based on the separation of KCLO3 from matches. What I would like to do is start with KCLO3, not matches.. Any ideas on what volumes to use? How much 3% peroxide added to XX? grams of KCLO3 mixed with XXml of water?






[Edited on 11-8-2011 by NHZ]

User - 10-8-2011 at 22:33

I suggest that you use the search engine, this subject is widely covered.
Also I would recommend to learn some basics before perfoming such rather complex synthesis.

NHZ - 10-8-2011 at 23:34

Well thats just it, I have tried to search and havent found anything regarding this particular method..


I have read several pages looking for this info, but to no avail.


Can you simply outline any potential hazards in this process? My main concern is being safe...

[Edited on 11-8-2011 by NHZ]

[Edited on 11-8-2011 by NHZ]

woelen - 11-8-2011 at 01:11

I made a miniature chlorate cell with MMO. It works very well:

http://woelen.homescience.net/science/chem/exps/miniature_ch...

NHZ - 11-8-2011 at 01:43

Thats a well put together writeup and cell, thanks for posting.
I tend to learn hands on, so the more visual reference, the better.

My cell is slightly larger, approx 1L or so, but I like the results you had with such a small vessel.

I have even seen guys making this in plastic yogurt containers..

Any idea if the procedure mentioned in the OP is somewhat safe as well?
I'm not too keen on finding anything out the hard way after some of the stories
ive read and pictures of shattered glass in skin etc..:o



woelen - 11-8-2011 at 01:53

That video is crap. Chlorate does NOT react with peroxide to make perchlorate!

Making perchlorte from chlorate cannot be done with MMO anodes, but it can be done with PbO2 anodes or platinum anodes. Another (more dangerous) option is to carefully heat perfectly pure KClO3 in a perfectly clean heat resistant glass apparatus until it just melts and then keep the temperature constant. Slowly the chlorate is converted to perchlorate and chloride. This latter procedure was used in the past as the main method for making perchlorate, but nowadays it is replaced by electrolysis with PbO2 or platinum anodes, because of safety concerns.

hissingnoise - 11-8-2011 at 02:02

Quote:
That video is crap. Chlorate does NOT react with peroxide to make perchlorate!

Chlorate does, however, react with ozone to form perchlorate but the expense involved makes it of academic interest only . . .

NHZ - 11-8-2011 at 02:03

Got it.. Guess that one officially falls under too good to be true.
I have read about heating it, but I also saw the warnings that accompanied that method.

I've been keeping my eyes open for platinum clad for the other method, and will just stick with that.

Perhaps an email is in order to the young gent who posted that video. With amateurs such as myself,
that video may lead to a false sense of security...

Thank you for the help :)

hissingnoise - 11-8-2011 at 02:14

Quote:
Guess that one officially falls under too good to be true.

Ozonised oxygen, fed to an actively stirred chlorate solution will slowly (ozone ouput is normally quite small) oxidise all of the chlorate to the perchlorate!

NHZ - 11-8-2011 at 02:52

What type of apparatus would be used for this ozone process?
Even a general idea would suffice. I may find it easier and less hassle
over hunting down and spending $$$ on platinum clad for such small amounts..

The best info I have found so far has been this gentleman's videos.

http://www.youtube.com/watch?v=O1aWzrRBMjk&feature=mfu_i...

plante1999 - 11-8-2011 at 06:50

If you can waith I will make a guide in 1-2week, if you cannot simply U2U me something and I will help you for making O3

From a apparatus that cost far less than 10$ CAN.

[Edited on 11-8-2011 by plante1999]

[Edited on 11-8-2011 by plante1999]

NHZ - 11-8-2011 at 11:10

That's sounds fine... I am in no rush, and to do things safely, its
better to take more time.

Is there a name for a common apparatus used in this regard? I
figure a HV source of some sort, but how its applied has me thinking.

If there is a 'name' or 'method' for the procedure you can give me,
I can start some reading on it now. Designing something is the easy part for me,
just need to know where to begin ;)

plante1999 - 11-8-2011 at 11:20

electrolisis of 15% H2SO4 with Pb anode.

[Edited on 12-8-2011 by plante1999]

NHZ - 11-8-2011 at 19:00

Quote: Originally posted by plante1999  
electrolisis of 15 H2SO4 with Pb anode.


Just for clarification, and pardon my ignorance.. Pb meaning a lead anode and what is the 15?

I have a rough idea, but cant picture the setup..

plante1999 - 11-8-2011 at 19:05

edited.

Simply make an leak free electrolisis cell and pass all the gas in a plastic tube.

NHZ - 11-8-2011 at 19:33

Quote: Originally posted by plante1999  
edited.

Simply make an leak free electrolisis cell and pass all the gas in a plastic tube.


Ahh, okay, that is making more sense..

So pass the gas through a saturate solution of chlorate?
Are there unique circumstances such as
temperature of the saturate and size of the bubbles?
Also what indication do I have of a successful conversion?

Please keep in mind, I understand the concept, but if the explanation
is too vague I get 'lost' :(

Thanks for the help by the way... I appreciate it :)


Edit:

Found an interesting cell design for those interested.. Though it
does use graphite, but still interesting none the less..

Link> http://www.thscience.no/dump/frogfot/synthesis/chloratecell1...





[Edited on 12-8-2011 by NHZ]

plante1999 - 12-8-2011 at 03:57

for an ozone cell:

Electrolise 15% H2SO4
Temperature should never get more than 35 degree celcius or an expolion will appen ( It appen 1 time to me) , lead anode is very important , you can cast lead piece inside a poly tube withch is buried in the ground.

Than you simply take a chlorate sollution ( usualy from a graphite aonde sodium chlorate cell and you pass for somes day O3 gas , slowly it will make NaClO4 , but if you want info about a chlorate cell I can help you.

NHZ - 12-8-2011 at 11:56

Interesting hazards on this one :o

I use sulfuric acid all the time for anodizing with obviously less
issues. I did some reading on the topic of ozone production and
found a few threads back to this site. I also found a .pdf with the
following diagram:




^ Is this along the lines of what im looking at? Its a bit of a setup
but im never in the mood for 'exploding' experiments..


Also found this:



Being a simpler solution, I may try this as well. Im assuming
there is no worry about an explosion if the gasses are collected separately?

Also what side cathode or anode) is the o3 produced?

[Edited on 12-8-2011 by NHZ]

plante1999 - 12-8-2011 at 12:45

If gas are separated no woory for explosion , O3 is produced at the anode (+).

polaris96 - 28-8-2011 at 12:10

I wouldn't try making the process above work if I were very new.

nstead, I'd use my electrolyisi cell in a two step process to produce sodium perchlorate from NaCl(aq) (or, even, in a one step process from purchased NaClO3) . Then, I'd take my NaClO4(aq) brine and dissolve some commonly available KCl into it. I'd agitate and filter the resulting mixture and then crystalize my KClO4.

I WOULDN'T worry about Ozone, H2SO4, or any other toxic/caustic/semistable or difficult processes at my entry level of knowledge. I'd put my nifty white KClO4 in a ziploc bag and STORE IT FOR LATER USE.

Then, I'd learn to extract Potash from wood ashes and then KNO3 from composted manure. I might, then, stroll down the avenue of black powder. After that, I'd Take out my H2SO4 and learn to make some HNO3. I wouldn't want to leave HNO3 sitting around, so I'd make a bit of nitrocellulose and informally compare the deflagration to that of the Black Powder I'd make previously.

Only then, with the theoretical ability to deal with both metathesis and Redox at a sophomore university level and the practical ability from more basic exercises, would I even consider opening the KClO4.

I know you didn't ask for the lecture, but that's the cost for a simple process to give you what you want. You want to make KClO4 instead of the commonly touted KClO3. That shows wisdom. Please be sure you're ready to use what you make safely.

BY the way, if you haven't read it, yet, pick up a copy a "Caveman Chemistry". I REALLY wish I'd had the damned thing as an undergrad.

Good Luck and Be Safe.


ps- I absolutely LOVE the look of those electrolysis cells in the picture. Think I may need to retool!
Graphite makes a decent anode if you don't mind a slow process, lots of time, and crappy efficiency. I use it a lot.
If you can get free electricity somewhere it's probably most cost effective. Expect your brines to get black and skanky if you use it. Not a problem so long as you're filtering before recrystalization.

[Edited on 28-8-2011 by polaris96]

[Edited on 28-8-2011 by polaris96]

hissingnoise - 28-8-2011 at 12:58

Quote:
I'd use my electrolyisi cell in a two step process to produce sodium perchlorate from NaCl(aq) (or, even, in a one step process from purchased NaClO3) .

Which type of anode would you use - I'm assuming you know that graphite anodes won't produce perchlorate?

bbartlog - 28-8-2011 at 16:25

Quote: Originally posted by polaris96  
Then, I'd learn to extract Potash from wood ashes and then KNO3 from composted manure [...] black powder ...

Uh, interesting advice. Have you done any of this stuff yourself? Or are you just encouraging someone else to screw around with premodern chemistry for your entertainment? The processes in question are really laborious; very poor learning-for-effort if education is what someone needs. That's not to say they're not worth doing if someone likes that kind of thing (and I do!), but as generic advice to someone this is kinda weird.

polaris96 - 29-8-2011 at 14:05

@ Hissingnoise. Very good point, sir. You actually can produce NaClO4 with graphite but it's messy and they get wasted really fast. I have done so. The platinum electrode NHZ mentions earlier is pretty good for the NaClo3 -> NaClO4 run

@NHZ: Swap your graphite electrodes for the platinum in the second run if you don't want a mess.

@bbartlog: Yes, sir, I've done all of it myself. I do confess lots of the advice comes from an epiphany I had after reading the book I suggested by Mr. Dunn. I think it's excellent advice for any chem student. I'm an EE not a Chemical Engineer. Chem was pedantic and exceptionally BORING to me as undergrad, so I'm not the guy who wondered what it would be like to make nitroglycerine after hours in my coffeemaker.

I had 0 interest in anything chemical, save the very specific interactions that govern semiconductor behaviour until a friend (a Chemical Engineer, herself) gave me the book and make me promise to work through it. Now I mess around a lot with chemistry. It's fun because of the history and because of the widget factor one gets from using common ingredients. So, I recommend the work to everyone.

Have I mentioned I also teach part time?

Bearing that in mind, please understand my chagrin at encouraging a novice to mess around with an H2SO4 brine and O3(g) when similar results could be obtained (albeit with a longer time investment) from a SALT BATH (point freely given about the graphite anode decomposing quickly generating NaClO4. But, he already has platinum, which will do it)

I suggested the approach above because it provides experiments of increasing complexity that allow the products of each to be employed in the next process. It's my way, not something I read about elsewhere. The early experiments (like extracting KCo from ashes) require little rigor but teach lab skills. the KCo can be used in the production of KNO3 etc etc etc. get it? He might even use the KCo produce KClO4 from NaClO4. At the end he gets HNO3, which is probably more useful than KClO4, itself.

You may not agree and I respect that. I think this is is a good way for a novice to pick up skills and aquire a few useful ingredients for later use. I DON'T endorse messing around with KClO4 as a way to discover the wonders of chem. I also think it's nutty to attempt a process as complex as the one shown above at entry level. That's not a rock thrown at bbartlog; I think the OP bit off a bit much for a first project.

So far as the premodern chemistry goes, that's what we're all doing here. KClO4 is readily available at about $7 per pound. We're not talking about making a rare and forbidden product, here.

bbartlog I hope you don't feel I've attacked you. I'm explaining why I said what I said. I respect you and realize I'm not a familiar face on this forum. Like NHZ, I'm here to see what else I can learn. Carpe diem

polaris96 - 29-8-2011 at 14:18

btw a quick search yields this link http://www.pyroguide.com/index.php?title=Preparing_perchlora... for some background on perchlorate cells. Amazing whats out there :p

EDIT: since I'm throwing out links, this is the one I used for inspiration when I was into making Chlorates http://webpages.charter.net/dawill/tmoranwms/Chem_Chlorate.h...

[Edited on 29-8-2011 by polaris96]

bbartlog - 29-8-2011 at 17:49

Quote: Originally posted by polaris96  


@bbartlog: Yes, sir, I've done all of it myself.

I suggested the approach above because it provides experiments of increasing complexity that allow the products of each to be employed in the next process.


In that case, well done and sorry if I seemed harsh. That notwithstanding, not everyone has enough wood ashes handy (nor manure, space and time) to do what you suggested; it takes a year or two to make nitre the old fashioned way. There are some modern tricks to accelerate the process but now you've wandered out of beginner territory...
Quote:
(like extracting KCo from ashes)


Do people really abbreviate carbonate that way? Seems dodgy (which is to say ambiguous though of course in this case we know what you mean...).
Quote:
I think the OP bit off a bit much for a first project.


Well, yeah. But nobody likes to be told they should be playing with vinegar and baking soda instead. And sometimes people (even newbies) can pull off the complicated stuff; mostly comes down to persistence, i.e. not having unreasonable expectations about how easy something will be.

BTW, if you have any information about your KNO3 project I would love to see it posted. I tried to do this once in a large flowerpot (and failed) and am about six months along with a much larger nitre bed, now using about a half ton of mixed chicken manure / straw / slaked lime. But I'm still far from sure I'll see any KNO3...

polaris96 - 30-8-2011 at 09:33

Apologies on the liberty with K2Co3 - I've been writing as KCo in my notes, which is sloppy. Again, not a chemist by trade.

Point well taken on playing with baking soda and vinegar (or drano and aluminum foil...) I had hoped that the simpler experiments I mentioned would be more interesting for a budding young pyrotechnician. Then again, I think balancing diffeqs can be stimulating, so take what I say with a grain of salt (your choice which kind)

So far as My KNO3 experiment goes I'm going to repeat it before I make a "real" post because it was 4 years ago and I wasn't taking great notes at the time. As I recall:

My main twist was using precomposted manure to assure the nitrification had already been taken care of, thus avoiding the real wait.

I made a large filter by flipping over a plastic carboy and cutting off the bottom. I stuck a microfibre colth over the mouth on the inside so the cloth lay well on both side s of the mouth. then I filled it with about 3" of mason sand. I ran water through this until the pH of the exit water was unchanged.

Then I made a slurry of the manure with limewater in a 5 gal pail (can't remember the ratios but it shouldn't be signifigant, so long as there's enough water to not get saturated. maybe 3 gal manure:2 gal limewater seems to make sense). I stuck a fishtank heater in it set to 70F (probably unnecessary) and let it sit overnight, stirring whenever I felt like it.

Next Day I poured the gack(no better word for it) through the sand filter. This is messy and I needed to muck out the filter a few times before I was done. I added a bunch of K2Co3 ( Actually, crude potash I had made earlier. The recipe. stipulated wood ash.). I stirred it and waited and hour for precipitation. I think I decanted it and left the last 1" or so of solution above the precipitate. It could just as easily have been filtered.

Then crystalized the KNO3. I can't recall the yield. It wasn't much but it was enough to make a couple of firecrackers (which I did later).

I took a twirl around the web, just now, to see if I had made any gross errors in recall. I'm surprised to have not found this method anywhere. I'm not sure where I got it from, now. It certainly isn't mine! (I'd love to take credit but I know I got it from someone else) . Iit seems a little modern for a "grandaddy's saltpeter" recipe.

Basically, the Calcium Carbonate goes to Calcium Nitrate and then swaps places with potassium as the K2Co3 is added, which immediately drops out of solution. I'll run the experiment again when I get time and post some pictures and proper quantities. It only took a weekend and it did work pretty well.


EDIT: Just worked out the metathesis (I get paranoid when I don't see lots of others doing something I've taken for granted these past few years)

Here we go:

1. NH4NO3 (already present in composted manure) dissolves in the limewater.

2. 2NH4NO3(aq)+Ca(OH)2(aq) => Ca(NO3)2 (aq) + 2NH4OH(aq)

3. filter and add K2CO3 (ash or chemical)

4. K2CO3(aq) + Ca(NO3)2(aq) => 2KNO3(aq) + CaCO3(s)

5. filter evaporate slowly, separate, recrystallize, etc etc etc.

I feel better now that I've worked out the reactions. As Mentioned I've done this but, well, you are a tough room :) I'll do it again and post more rigourous details when I get some free time <rueful sigh>


[Edited on 30-8-2011 by polaris96]

Last few edits werte to clear up my awful arithmetic in the metathesis coefficients


[Edited on 30-8-2011 by polaris96]