making potassium (per) chlorate

[WSM]

WSM..

I have to say thanks for your inspiration. I hope youll forgive me for bumping in here, but your advise on the spot welder was a good one... I tried the cheap $20 spot welder attachment for a arc welder , and it did nothing but burn and imbrittle the TI. I managed to get a halfway weld with it, but it was a waste of $. I just purchased the 115V pincher style spot welder, and it worked like a dream......! Almost effortless. One thing that I have learned is Ti needs to be absolutely clean and acetone washed before a weld to achieve a great bond.

Thank you again .

Pyrojig

 

Hi pyrojig,

 

You're welcome. I recommended it because I use it myself and I know it works. I'm glad you're happy with it and I'm happy to have helped.

 

WSM

[WSM]

also, the setup you described, you mean have one cathode on either side of the anode right?

 

Well, The ideal setup is to use equal areas on either both sides of the anode to fully utilize the surface area of the anode. True, the outsides of the cathodes aren't fully used but they're easier to come by than MMO coated titanium anodes. My little run a few weeks ago used cathodes to surround the anode and I got the best performance from my MMO to date. If you can get more CP titanium, try it the way I describe and see what you think...

 

WSM

Edited August 17, 2011 by WSM

[WSM]

i just used tap water, since i was just throwing together a cell since i finnaly was able to. should i use deminieralized water instead?

i just wasted 3 hours of effort , a peice of filter paper and a good stainless steel pot in removing the precipitant.

the pot is now full of little eroded holes, after my mum insisted we just let it sit for 30 mins. the solution turned dark brown, and had eaten small holes in the pot upon my return.

the chlorite somehow dissolved the iron in the pot to make iron chloride, which as soon as i ran the cell, formed black iron oxide, which gave me a big fright since i thought my anode was producing the mess, since the water was clear when i begun , well actually it was yellow i asumed it was aqueous chlorine though, since all my past cells went yellow over time.

anyway, i am going to start a fresh batch now. and this time ill use boiling hot water instead of cold water to dissolve the chloride.

 

I'd suggest trying it with demineralized water first and establish a baseline to compare other runs to thereafter. Salts dissolve faster with moving water. Stirring works and so does heating; both together is even better, but either alone works just fine.

 

I had a cheap stainless steel mixing bowl turn into a sieve because of ferric chloride solution. What a mess (haven't done it since).

 

WSM

[oldmanbeefjerky]

well i just ran it overnight and i have have discovered the anode heating problem isnt that bad, it didnt get any hotter then 55C, and also my hotmelt glue is not chlorine proof so i need something else to fill the cathode plate holes with . all in all, its working fine. the ampergage even rose overnight from MAX 15A to 19A

 

WSM, the pot i used because it was actually rather good stainless. but it seems i was wrong, now i have to buy a new pot.

Edited August 18, 2011 by oldmanbeefjerky

[WSM]

WSM, the pot i used because it was actually rather good stainless. but it seems i was wrong, now i have to buy a new pot.

 

Oops! I hope your Mum forgives you (you better get her a good one ). Congrats on getting the cell started.

 

WSM

[oldmanbeefjerky]

i have fixed it , hopefully for the last time too,

 

i drilled a hole into the anode plate and attached a bolt which i am using to clamp the copper wire onto the anode. im fairly certain it will last. just to be sure, ill add some wire glue.

 

 

i must ask though, what is a good sealant to use to stop chlorine gas leaking out from the holes where the electrodes come through the lid, i am trying hot melt glue, but it turns brittle and gets pushed aside rather quickly, and for some reason gas doesnt seem to want to leave via the vent tube i have put in the cell.

 

also

i just found out i could have used my ozito tool (like a dremel), or my dads angle grinder, to cut up my sheet instead of using the plasma cutter which was quite messy.

the rotating grinding disc will easily cut through CP titanium like it would steel. well, i still have one sheet left , when i cut that one up to sell the anodes ill be sure to use the angle grinder instead!

[WSM]

i must ask though, what is a good sealant to use to stop chlorine gas leaking out from the holes where the electrodes come through the lid, i am trying hot melt glue, but it turns brittle and gets pushed aside rather quickly, and for some reason gas doesnt seem to want to leave via the vent tube i have put in the cell.

 

Try silicone caulk. It's not permanent but may last for a few runs. The reason I went with tubular leads and compression fittings was to prevent the problems you describe. I was tired of my electrical connections getting eaten away. Perhaps your vent tube isn't large enough, try a larger diameter tube.

 

I like the idea of cutting the titanium with a Dremel tool. I'll have to give that a try, but recommend goggles and a good respirator. Thanks for the idea.

 

WSM

[pyrojig]

Try silicone caulk. It's not permanent but may last for a few runs. The reason I went with tubular leads and compression fittings was to prevent the problems you describe. I was tired of my electrical connections getting eaten away. Perhaps your vent tube isn't large enough, try a larger diameter tube.

 

I like the idea of cutting the titanium with a Dremel tool. I'll have to give that a try, but recommend goggles and a good respirator. Thanks for the idea.

 

WSM

 

If you don't mind me asking, what size tube do you run for your sys ?

I have a combined 3/8in for the exhaust on my 5gal sys....is that enough?

[WSM]

If you don't mind me asking, what size tube do you run for your sys ?

I have a combined 3/8in for the exhaust on my 5gal sys....is that enough?

 

That depends. Do you smell fumes or see large amounts of salt creep? If so, consider using a larger vent tube. If not, don't worry about it.

 

WSM

Edited August 19, 2011 by WSM

[pyrojig]

Nothing like that .....I just was wondering... I had a strange thing happening where the need for acid was remarkably low and the cell was running hot 50*c+ .. I know this adds to the efficiency, but it seems like swede was running more acid with a similar setup....

 

Another Q... Is I have a 30A PS supply and I want to make sure not to overload it..( but max out the amount of Amps I can get)

 

*.. Is 25A safe to maintain... and can I go up to 28A w/o any dangers of losing my PS.?

Edited August 19, 2011 by pyrojig

[Bonny]

That depends. Do you smell fumes or see large amounts of salt creep? If so, consider using a larger vent tube. If not, don't worry about it.

 

WSM

 

I always have salt creep even with silicone as a sealant, rarely smell any fumes though. I use a 1/2" pex pipe as a vent tube on an 18l bucket cell.

 

 

 

Nothing like that .....I just was wondering... I had a strange thing happening where the need for acid was remarkably low and the cell was running hot 50*c+ .. I know this adds to the efficiency, but it seems like swede was running more acid with a similar setup....

 

Another Q... Is I have a 30A PS supply and I want to make sure not to overload it..( but max out the amount of Amps I can get)

 

*.. Is 25A safe to maintain... and can I go up to 28A w/o any dangers of losing my PS.?

 

My (PC) power supply is only rated for 20A, but I've run it at almost 25A for weeks at a time and it's still fine. I ran 5 or more batches of chlorate with it.

[pyrojig]

I always have salt creep even with silicone as a sealant, rarely smell any fumes though. I use a 1/2" pex pipe as a vent tube on an 18l bucket cell.

 

 

 

 

 

My (PC) power supply is only rated for 20A, but I've run it at almost 25A for weeks at a time and it's still fine. I ran 5 or more batches of chlorate with it.

 

That still leaves me wondering( I know it can be done)... No offense , but I dont want to fry this PS. When I first fired it up it was cranking 38A !!! It is only rated for 30A... My electrodes where too close apparently ( like 3"or so) .

 

I can score more for fairly cheap , but it is a pain to convert( couple hours of soldering etc.). I Have the electrodes spaced 6" apart and it is at 25A . The electrodes are 3in x 10in TI and MMO.

 

[oldmanbeefjerky]

i will try silicon calk, i wish there was a more permanent sealant i could use.

i am getting a bit of salt creep as well, though. from what i hear though this is normal. but just to be safe i might set up a fan to blow onto my cell, which might even cool it down a bit and will blow away any rogue chlorine.

 

also,

i think i have an answer for why hotter cells are more efficient, i might have said this before, but im not certain.

as you know, chlorite or hypochlorite can be made by passing chlorine gas through hot hydroxide solution.

for the chlorine to react, it must become aqueous though. like most water soluable substances, i think more chlorine can stay dissolved in the water when it is hotter. and the hot hydroxide becomes more reactive and is reacting faster with the chlorine, meaning less is released as gas. Im fairly certain that heat catalyses hydroxide reactions.

 

I like the idea of cutting the titanium with a Dremel tool. I'll have to give that a try, but recommend goggles and a good respirator. Thanks for the idea.

 

only the cutting/grinding blade works. i tried drilling and it wont work. however brass drillbits on a regular power drill seem to be able to get through the sheet ok, but slowly.

 

 

also, pyrojig

 

on my old powersupply, it said "Max Continuous current".

i think the powersupplies can produce allot more than they are rated for, but will slowly overheat, though most include thermal overload protection.

their max amperage is the maximum they can handle running non stop

Edited August 19, 2011 by oldmanbeefjerky

[Mumbles]

Excellent use of capital letters there

 

also,

i think i have an answer for why hotter cells are more efficient, i might have said this before, but im not certain.

as you know, chlorite or hypochlorite can be made by passing chlorine gas through hot hydroxide solution.

for the chlorine to react, it must become aqueous though. like most water soluable substances, i think more chlorine can stay dissolved in the water when it is hotter. and the hot hydroxide becomes more reactive and is reacting faster with the chlorine, meaning less is released as gas. Im fairly certain that heat catalyses hydroxide reactions.

 

 

 

 

Have you ever had a chemistry class? Gases become much less soluble with increasing temperature. One of the methods to degas solvents is to boil them, though it is not great. Heat isn't and never will be a catalyst.

 

I've been thinking about this increase in efficiency, or at least the lower acid demand for the past week or so. I came up with something at least plausible. Heat can convert hypochlorite, and probably chlorite to chlorate on it's own. This certainly works in boiling water. A 50C+ cell might be doing this reaction to some degree on it's own. This would actually reduce the pH naturally. The more oxygen atoms you get on the chlorine atom the less basic the ions are. You'd be going from 3 fairly basic hypochlorite ions to 1 chlorate and 2 chlorides both which should be close to neutral.

Edited August 19, 2011 by Mumbles

[oldmanbeefjerky]

That does sound more plausible ,

 

By the way, just a few minutes ago i went to check on how my new tactic to stop that salty crust creeping up my electrodes and onto my connections, which was to smear some grease around the plate which i would hope would stop the salt as it would with a trail of ants.

Anyway, when i checked i noticed something very odd, i couldn't smell any chlorine!

I took a whiff of the gas coming from the vent tube ( not directly of course), and the chlorine smell was very weak, like smelling pool water. I went to the bathroom just to make sure my sense of smell hadn't been deadened , since the bathroom had been cleaned with bleach a week ago, i could still smell the bleach smell there.

Does anyone have an explanation as to why my cell is emitting less chlorine?

It's not really a bother to me, im just curious, or do all cells just make more chlorine if the first day or so than they do later on?

 

-edit-

 

 

I see that the cell is starting to make noticeable amounts of chlorate now, there's a good tablespoon precipitated out of solution right now and the crystals are even forming on the anode which was delightful to see, and the cell is so hot it hurts to touch for more than 2 seconds, so im guessing there is much more dissolved in there!

since so little chlorate has formed, but the amount of chlorine released has dropped, i want to know if this is normal? The amperage hasnt really dropped much at all over the last few days, its always hovered around 10-16A , when it was at a maximum 20A i suspect most of it was due to the high resistance of the old contacts.

Edited August 19, 2011 by oldmanbeefjerky

[ausfire]

That does sound more plausible ,

 

By the way, just a few minutes ago i went to check on how my new tactic to stop that salty crust creeping up my electrodes and onto my connections, which was to smear some grease around the plate which i would hope would stop the salt as it would with a trail of ants.

Anyway, when i checked i noticed something very odd, i couldn't smell any chlorine!

I took a whiff of the gas coming from the vent tube ( not directly of course), and the chlorine smell was very weak, like smelling pool water. I went to the bathroom just to make sure my sense of smell hadn't been deadened , since the bathroom had been cleaned with bleach a week ago, i could still smell the bleach smell there.

Does anyone have an explanation as to why my cell is emitting less chlorine?

It's not really a bother to me, im just curious, or do all cells just make more chlorine if the first day or so than they do later on?

 

-edit-

 

 

I see that the cell is starting to make noticeable amounts of chlorate now, there's a good tablespoon precipitated out of solution right now and the crystals are even forming on the anode which was delightful to see, and the cell is so hot it hurts to touch for more than 2 seconds, so im guessing there is much more dissolved in there!

since so little chlorate has formed, but the amount of chlorine released has dropped, i want to know if this is normal? The amperage hasnt really dropped much at all over the last few days, its always hovered around 10-16A , when it was at a maximum 20A i suspect most of it was due to the high resistance of the old contacts.

 

The smell of chlorine should only be present during the start of the run. At the start of a run the pH should be somewhere around 7, as the cells reactions begin to take place Chlorine gas is produced and allowed to escape the cell causing the pH to rise. As the pH rises less and less Chlorine is able to escape the cell up until the point at which the cell becomes "stable", generally around pH 10 I believe. I remember seeing a diagram that displayed this process a hell of a lot better then I can explain it but I couldn’t find it. This is all assuming your cell does not contain pH control.

 

 

 

 

[oldmanbeefjerky]

So if i keep it near neutral, 7, it will make allot of chlorine then.

Is this why allot of guides say improvised chlorate cells work better if you add hydroxide , which increases yield?

 

 

Also, this is rather urgent. i need to know, if it is safe to leave the cell turned off for 3 days with the electrodes sitting in it, my dad is back from the mine isnt particularly fond of anything he doesnt understand, like science, chemistry, dragging and dropping songs from his laptop to his ipod, gravity, and most sciency things in general!

Ive packed away my cell, but have left the electrodes in it, i just need to confirm that they wont break or degrade.

Edited August 19, 2011 by oldmanbeefjerky

[WSM]

Also, this is rather urgent. i need to know, if it is safe to leave the cell turned off for 3 days with the electrodes sitting in it, my dad is back from the mine isnt particularly fond of anything he doesnt understand, like science, chemistry, dragging and dropping songs from his laptop to his ipod, gravity, and most sciency things in general!

Ive packed away my cell, but have left the electrodes in it, i just need to confirm that they wont break or degrade.

 

It would be best to take the electrodes out of the cell liquid while denergized. After the last run, I removed my electrodes, rinsed them and stored them dry. One of our European contributers mentioned how his cell was acting poorly after power outages during his run.

 

WSM

[oldmanbeefjerky]

Oh!

darn, Ive left my cell turned off for 4 hours now. id' best sneak off and remove the electrodes from the cell when my dad wont notice.

 

-edit-

I was completely amazed at how much chlorate precipitated out of solution when the cell cooled down, being off and all,

but because i had to be sneaky, i wasnt able to photograph the cell, only the electrodes attached to the lid which i took inside.

anyway, what i had there sitting on the anode was far more than i had ever gotten ever trying other methods like the bleach method, using pool chlorine and a soluable potassium donor, and electrolysis using copper at first , and then with carbon rods which seemed to be going well (was running at 5v less than 200ma roughly), which filled my room up with chlorine smell, then again with carbon rods, which gave no yeild, since i hadnt done my research right and in the proccess of extracting the chlorate, expected chlorate to precipitate out, but in fact i precipitated chloride and discarded chlorate by accident, the same thing happened with lead, which now that i think about, actually would have yeilded more chlorate than i have now, with a rather easy to clean up mess. This has been my first ever run with potassium chloride.

 

 

Anyway, i am super happy.

what i have sitting in the bottom of the cell, in volume matches the amount of chloride i put into the cell, but being big square crystals, is not it exactly. i recon i have got 20-80g chlorate so far, out of an expected 400g. including what i have from the anode .

just to be clear, the crystals formed on the anode as the cell cooled, the crystals that formed during electrolysis were much smaller and unnoticeable on camera

Edited August 19, 2011 by oldmanbeefjerky

[hillbillyreefer]

Excellent news OMBJ. Instead of reading about it, doing it is quicker and gets results, same thing happened here. My first batch is going to get it's first recrystalization today, I hope, it's been sitting in the bucket for a week. I'd like to get another batch rolling today.

 

Never leave your electrodes in the liquor without current.

Edited August 19, 2011 by hillbillyreefer

[oldmanbeefjerky]

well, they dont look damaged, so i think im ok

funny thing is that my cell current hasnt dropped even slightly, so the cell has much more electrolysing to go.

Can i scoop out the crystals though that have formed? or should i leave them in? since they will redissolve when the cell heats up.

[hillbillyreefer]

I thought my cathodes were ruined, they had no power for several hours and corroded. They are 316 stainless steel, I soaked them in a product called Evaporust overnight. They came out looking brand new, no corrosion is visible on the them. Restarted the cell with fresh liquor tonight. Now to clean up the chlorate from the original run.

[oldmanbeefjerky]

ooh, tell me if your liquor turns black-brown, thats what happened to me after it got some iron dissolved.

[hillbillyreefer]

The first run was clean until the power was disconnected for an unkown amount of time, a maximum of about 8 hours. The 316SS was corroding when I discovered the power was out. I left it run for several more days. The iron oxide settles out of the solution, so when that happens I'm decanting to get rid of it, then recrystalize the chlorate. Kind of a pia. The second run is only a few hours old, no black crap yet. Hopefully with no power failures there won't be any. Will let you know.

[oldmanbeefjerky]

did the solution turn yellow?