Sciencemadness Discussion Board

Sodium!

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Quantum - 29-4-2004 at 17:00

patu seems to have a good small scale idea for sodium. However then Tacho got hot NaOH on his person; thay does not sound very fun. I just want a few beads of Na nothing fancy like you guys at least not yet.

Has anyone tried patu's method besides Tacho and can they provide more detail?

Tacho - 30-4-2004 at 03:21

Bromic acid's method seems the easiest so far. If an iron (steel) wire can be used as electrode it would be even more simple.

About Patu's way, I must say that my lab techniques are sloppy and hurried, and I used Cu wire as the loop electrode.
For what I have seen so far, though, electrolisys of molten NaOH is an intrinsically messy procedure. It pops and fizzes a lot.

Edit: A try of Bromic's method using a small iron loop as electrode would be a nice experiment.

[Edited on 30-4-2004 by Tacho]

patu - 30-4-2004 at 15:59

I must admit that its does pop the newly made sodium out of the crucible. the cool thing is, is that it calms down greatly after about a minute and a half. After that the molten sodium quietly forms waiting to be dunked in the mineral oil. For the more reactive part of it i'm suited up in a heavy coat and a welder's mask and gloves.

Quantum - 30-4-2004 at 17:53

Patu! You realy should post more; you seem to have lots of interesting ideas. Perhaps you just read 99% of the time.

Thanks for the information. I think I would just stay far away for the first few mins!:o

Edit: Are you running it on a hot plate or a flame? Do you hold it just above the mp of NaOH or much hotter?

[Edited on 1-5-2004 by Quantum]

The_Davster - 30-4-2004 at 18:41

When I made my bit of sodium I found that it was best to melt the sodium hydroxide over a burner, then once molten remove the crucible from over the burner and quickly place the electrodes in and turn on the power, the current kept the area between the electrodes molten. When I was done I decided to see what would happen if I heated it again. In under a minit the sodium blob had dissolved into the sodium hydroxide.

patu - 1-5-2004 at 20:57

I use a hot plate when I make sodium. I dont even own a bunsen burner. the methods I use are very crude yet very effective. I have little bottles full of sodium and sodium/potassium alloys thet I have made.

BromicAcid's use of resistance heating

Strepta - 6-5-2004 at 17:28

I've been following this topic for awhile and have tried several experiments. Just this evening I tried Bromic's experiment using a watch glass, OTC Red Devil Lye and two electrodes made of Ni 200 sheet metal. I started the reaction using a propane torch then turned on the power which was an 0-14v, 0-5 amp bench power supply. Spacing between electrodes was approx. 1cm, depth a few mm. the initial curent was 1-2 amps (fluctuated a lot) and stedily increased to about 4 amps as the H2O was electrolyzed out. In a few minutes the sparks began to appear, then the first shiny globules of Na. My experience was almost identical to that described by Bromic. As to chemoleos questions, I suggest that the phase change (solid-liquid) interface which is enabled by resistance heating keeps the temperature right at the melting point, not allowing it to climb to the point where the Na becomes soluble forming the metalloid. Also, all molten material is in the vicinity of the electrodes--becoming solid 1-2 cm away--this protects the glass from attack by the NaOH. All in all a very impressive little demo made more so by the minimum of fixturing required. Haven't yet found a very effective way to remove the Na; may try the wire loop suggested by PATU. More later...

Look! For I have found good infomation

Quantum - 8-5-2004 at 19:13

SAS Chemistry Guide to making small amounts of Sodium

They decribe in good detail the proccess that patu uses . They use a burner instead of a plate but they even use a 'tin' can. Worth reading to all interested in making small amounts of sodium.

Im going to try it tommorow!:D

Bromic's technique with patu's wire loop

Strepta - 9-5-2004 at 04:30

I replaced the nickel sheet metal cathode with a loop of iron wire (.35 cm dia.). This allowed me to capture almost all visible Na. ;) I hold the loop with a gloved hand--yes, molten NaOH is nasty-- and work it around the melt to get the Na inside. I then lift it out and slap it against the test tube containing motor oil (just because it was nearby). I ran the setup this way for an hour, removing the little balls of Na and quickly returning the loop to the melt. I was usually fast enough to get it back before the NaOH solidified. I kept the propane torch on low flame nearby so if I was too slow, I could re-melt and be making Na within a few seconds. this technique seems to work acceptably well (at least for me) to make small amounts of Na. I'm still amazed that a mere 35 watts in ( I'm running this setup at 10V and 3.5 A) is enough to keep the melt at 315C without any attempt to insulate from ambient. :o I have not yet perfected a way to clean up the Na that is produced. I've melted it under paraffin, xylene and ordinary paint thinner, all three of which result in shiny balls of Na but there is still come contamination (NaOH) visible each time. Ideas welcome.

BromicAcid - 9-5-2004 at 05:38

Quote:

I've melted it under paraffin, xylene and ordinary paint thinner, all three of which result in shiny balls of Na but there is still come contamination (NaOH) visible each time. Ideas welcome.


You need an inert liquid with a density of 1 g/cm3 or above with a boiling point of greater then 100C. This is the technique used to purify lithium that I mentioned before, you melt the impure NaOH/Na mixture at the bottom and as it melts the pure-er Na will float to the top leaving the NaOH behind. You could use something like nitrobenzene possibly. I think most chlorinated hydrocarbons will react with Na at these temps and that is the massive drawback because most organic liquids that have a density of greater then 1 are halogenated hydrocarbons.

[Edited on 5/9/2004 by BromicAcid]

Chemical burns!

Quantum - 9-5-2004 at 07:35

I tried the sodium making using a spoon on my hotplate. After it melted I stuck a 9v transformer wires into it but nothing happened. I was convenced that it was dead so I put the 2 wires on my tough to see if it would 'tingle'. Sadly the wires had a little bit of NaOH on them!:mad: I had to wash my mouth out and now I have a little burn. I used a diffrent PSU(5v 20a) and I saw a little sodium but I could not collect it. I think its redisolving in the NaOH even though I turned off the plate and lifted the spoon off it when I applied the current.

In a way I failed but I did see a speck of shiny Na!

Saerynide - 9-5-2004 at 07:40

You freak!!! Dont lick live wires, no matter what the voltage is!! :o

To test if a PSU is working just shove the wires into tap water and see if it bubbles :P

[Edit:] Im sure you know this already, but you should try to *show* it :P

[Edited on 9-5-2004 by Saerynide]

Quantum - 9-5-2004 at 07:50

I don't know what I was thinking!:P The sad thing was that I had a multimeter sitting on a bench 5 feet from me the whole time. I didn't get much sleep last night.

Tacho - 18-5-2004 at 04:04

Quote:
Originally posted by Cyrus
I have gotten NaOH on my tongue too,
(snip)

4!

I have used thin ss pots to melt NaOH, and used the pots as anodes (not where Na forms). That's about 10 to 20 minutes of exposure. They withstand it, but were dark grey/black where exposed. I must say I could never make sodium by electrolysis.

I read somewere that type 304 ss will dissolve in molten NaOH. The information itself is probably useless, but the key idea is that there are different ss, with different properties.

My Results

hodges - 5-6-2004 at 14:04

I recently bought a power supply that is capable of putting out either constant voltage or constant current. It will put out any voltage from 0-30V and any current from 0-5A.

So I decided to try some NaOH electrolysis. I placed some NaOH in an empty metal food can. I used the can as the anode and an ordinary copper wire as the anode. I slightly wet the NaOH and then turned on the power supply. I found that a current of about 1A, which was about 10V, was required to keep the NaOH melted enough to conduct. So I set a current of 1.5A, which was about 14V. There was, of course, a lot of bubbling from the cathode, and occasionally an orange sparkle would rise from the cathode into the air. Kind of like when you light a blowtorch and some of the gas in the air from before you lit it burns above it. There were also occasional pops of exploding hydrogen, accompanied by a yellow flame. After a few minutes, I could see the shiny sodium floating near the surface of the melted NaOH at the cathode. After another minute or so, there was a loud crack and two orange glowing pieces of molten sodium shot into the air. After that, there were smaller cracks regularly at about 10 to 15 second intervals. Apparently the sodium was shorting between the electrode and the can, resulting in the regular pops. At this point I turned off the power supply.

I waited for the NaOH to cool. But when it did, I was surprised that I didn't see nearly as much sodium as I expected. There were a few small pieces inside the NaOH, which I chipped away, but not much. I added water to the can and got quite a bit of fizzing, though, along with large orange sparks. Also there was a small amount of sodium left on the cathode wire, and when I put a drop of water on it there was quite a bit of fizzing.

At that point, I cleaned up the mess, and put away the power supply. But then after everything was put away, I noticed what appeared to be two drops of foam on the side of the metal sink. These drops were slowly bubbling. I picked one up on the end of a popsicle stick, and sure enough it looked like metal surrounded by the foam. I dropped the small one, about the size of a pinhead, into water and it fizzed. I then dropped the larger one, about the size of a small BB, into the water. It skated back and forth on the surface of the water, gave off large orange sparks, and finally "popped" away from the surface of the water when it was all nearly consumed. The biting smell of NaOH vapor in the air was noticable nearby.

Later I tried a similar experiment using a glass container and steel wires for the electrodes. I found it much harder to maintain the current flow, and it took over 20 volts just to get an amp of current. There were no explosions, but every few minutes the sodium would burn at the cathode, for several seconds accompanied by a yellow light and a decrease in conductivity. Upon cooling, I had no sodium to speak of. The solid mass did not react with water, and there was just a small amount of fizzing when putting the cathode wire into water.

However, I did notice something strange in the second experiment. The steel anode wire was eaten away considerably (about 1/4 inch of it was gone). Near the anode, the NaOH had a dark purple color. I'm wondering if the steel has manganese in it, and KMnO4 was formed. I know manganates can be formed from oxides of manganese in melted alkalis, but I thought these were usually green until acidified.

BromicAcid - 5-6-2004 at 15:48

Quote:

The steel anode wire was eaten away considerably (about 1/4 inch of it was gone). Near the anode, the NaOH had a dark purple color.


Anodic oxidation of iron to ferrate, I've been experimenting with this lately, seems to work reasonably well, color changes are significant and usually somewhat quick. Acidification will result in almost instataneous gas evolution from decomposition of ferrate. That is why I choose nickel as my number one electrode material in hydroxides.

hodges - 6-6-2004 at 12:18

Would iron ferrate be purple though?

------------------------------------------------

YES. Look for the ferrate thread and keep this on topic please.

[Edited on 6-6-2004 by vulture]

The_Davster - 6-6-2004 at 12:29

Hodges; I have found it best to remove the sodium from the sodium hydroxide while it is still molten. Upon solidification, some of the sodium seems to be absorbed into the sodium hydroxide.

BromicAcid - 6-6-2004 at 17:31

Sodium is much more soluble in cooler hydroxide then hot. For example, 25.3 g of Na will dissolve in 100 g of NaOH (l) @ 480C but at 800C only 6.9 g will dissolve. The papers I have say the solubility increases consistently to the solidification point of the hydroxide melt and therefore it is more economical to remove the Na before cooling the melt. (However if you run your melt too high you increase cell corrosion and decrease yeild by having the sodium react with it's hydroxide so there is some give an take, however I believe it is the general consensus to run the cell at as low a temperature possible.)

To remove your sodium you could try a chilled iron wire, upon touching the surface the sodium should freeze to it and be able to be scraped off, sorry if I've mentioned this method before.

Some information relating to the actual electrochemical process and reason for low yeilds:

"The hydroxide is electrolyzed
NaOH ---> Na + OH-
the sodium appears at the cathode and, at the anode, the hydroxyl is resolved into water and oxygen. The hydrogen that appears at the cathode is the product of a secondary chemical reaction, between the sodium at the cathode and water formed at the anode. It is therefore possible to have both hydrogen and oxygen liberated at the anode, and explosions may result..... The sodium which diffuses to the anode may also react with the oxygen there being evolved, forming sodium peroxide, and the later may react with more sodium forming the monoxide."

So wouldn't it be possible to add more water to the mix to react away the Na2O2 and such thereby increasing overall yields? Although adding H2O to molten hydroxide would be a bad thing, commercial hydroxide has appreciable water in it so just adding some of that could add the necessary water to hydrolyze the oxides of Na to the hydroxides and keep the yield high correct? However this would only be a matter of concern in large scale projects.

(500th post, I am the first International Hazard!) :D

[Edited on 6/7/2004 by BromicAcid]

Marvin - 7-6-2004 at 10:53

Where does the sodium solubility data come from? Its not what I'd have expected. Having said that, it shouldnt really be relevent as to succeed you have to be operating the cell only just above the melting point of the lye.

Either 7 or 12% of carbonate improves the yeild (I forget which and nolonger have access to the book).

The idea about adding water to react with the sodium peroxide forming at the anode is..... questionable. You said yourself water is forming at this electrode anyway, and its a bad thing because it depletes the sodium produced by diffusion.

BromicAcid - 7-6-2004 at 13:32

The data came from the "Complete Treatise on Inorganic Chemistry" in the section about the isolation of the alkali metals. Additionally 1 - 3% NaCl is supposed to improve yields in a castner cell but cell corrosion increases dramatically every percent so there is a massive tradeoff.

Esplosivo - 9-6-2004 at 08:43

Sodium borate, commonly found as borax, seems to be as good as sodium ethanoate for molten electrolysis. It has a melting point of 75 deg Celcius, and is said to be easily available, though I cannot find it still. The sodium formed would be in the solid state. Would this work out? Thanks

The MSDS of sodium borate

Edit: What would form at the anode of such a cell?

[Edited on 9-6-2004 by Esplosivo]

chemoleo - 9-6-2004 at 08:55

Lol, that's a mistake that has been done before :P (see sodium acetate etc)

Your sodium borate contains crystal water, Na2B4O7 . 10H2O - and you can imagine what happens to the nascent sodium once it contacts water...

Esplosivo - 9-6-2004 at 09:50

Yes right, my bad. If may I ask, can't the sodium borate/acetate by dried, like for example heating in a microwave like other normal ionic salts. I know excessive heating will result in decomposition, but will removing the water require heating to such high temp for the salt to decompose?

Edit: I've found out that sodium acetate loses the three water molecules from the trihydrate form at a temp of approx. 123 deg Celcius and decomposes at a temp above 300 deg celcius. Two different MSDS sheets give different melting points of the anhydrous acetate. What is it really - 58deg Celcius or 324 deg celcius?

Edit 2: Sorry for the stupid question. Just found out that at such a temperature both the acetate and the water will be in the gaseous state and therefore cannot be seperated.

[Edited on 9-6-2004 by Esplosivo]

[Edited on 9-6-2004 by Esplosivo]

hodges - 9-6-2004 at 15:09

Usually when I see a low "melting" point for a hydrated salt I find that the "melting" is actually the water being released, which the less-hydrated salt then dissolves in.

froot - 18-6-2004 at 08:24

Here's a slight mod to Patu's method I tried with promising results. I've put in pics, hope you can access them. (PS. please can somebody u2u me the procedure for placing a pic directly onto the post using the code in the FAQ or upload it to the board, thanx)

This may have been discussed before but I've found that current density plays a major role in results. I used a 5V 50A supply and the more cathode I have in the molten NaOH, the less Na I get. It seems that the more voltage I need.

In the first pic youll see the setup I used. The cathode is a ceramic tube about 10mm ID with a piece of fence wire through it with the tip just protruding from the business end. (2nd & 3rdpic).

This was inserted into the melt as deep as possible without touching the tin obviously. After 5mins I carefully removed the tube and gave it a shake over some paraffin. Out popped a generous blob of sodium. (4th pic).

Na setup.JPG - 78kB

froot - 18-6-2004 at 08:27

pic2

Cathode1.JPG - 31kB

froot - 18-6-2004 at 08:29

pic3

Cathode2.JPG - 30kB

froot - 18-6-2004 at 08:31

pic 4

Sorry about the mess Vulture.:(

Sodium!.JPG - 82kB

Tacho - 18-6-2004 at 08:38

Congratulations!

I'll PM you about pictures.

Today was running the Castner Cell day!

BromicAcid - 15-8-2004 at 17:07



The design, a cast iron pot with a hole drilled in the bottom though which a steel pipe was put, it had a large nut on one side and the other had an end cap that I cut in half, in between I used a silver washer. I put a nickel wire into this pipe and held it in place with some two part epoxy then when it hardened I melted some NaOH separately and poured it into the hole. I drilled a hole though my electric range burner to accommodate the pan sitting on it with the whole pipe going into it, in the picture above on the left you can see just the nickel wire coming out of the bottom of the range. That is where I connected the wire for the cathode.

I had half of a lid on the top with an adjustable nickel anode. Also in the top left hand picture you can see my 'bell' that had a top held on by a hinge.

Initial heating was attempted with a MAPP gas torch but it was not going fast enough plus the CO2 and H2O rising up from the combustion was seemingly quickly absorbed by the NaOH so I just set it on the hot plate and heated on high heat.

Surprisingly the hot plate managed to melt some NaOH in the bottom and I plunged the anode into it and started electrolysis which in turn heated the mix with resistance heating. Now nothing seemed to happen for a while, it did react with the coating on the pan though, it turned the NaOH slightly red.

Eventually everything melted and the anode depth was adjusted so that it could run at 12V and not blow a fuse. The amps were over 15. But the bell shorted out and Na was forming on the outside without my knowledge. That brings me to picture #2. Well, at least it was pretty.

For the rest of the experiment explosions occasionally blew the top off the bell. I got a small amount of Na recovered, ~2g but it does look like a lot considering the low density, but it's nothing considering the 1.5 kg of NaOH used in the cell.

Then it started raining bad, see attachment. Rain falling into molten NaOH was NOT my idea of a fun time, but what the hey, I kept going for over an hour.

But when I decided to stop I took the super hot pan and tried to pour it into a different pan. This was a pain because I forgot there was a pipe running though the hot plate, and it was cast iron so the handle was ultra hot. When I finally finagled it out I poured into the pan which now had significant rain water in it and NaOH exploded out! Molten NaOH spattered on my arms and shirt and table, the table promptly charred and attempted to catch on fire.

Even though it was burning my hand I forced the cast iron pan back into the burner and gave up for a bit.

Much later when it stopped raining I cleaned up my pan, the cast iron, after 4 hours on the hot plate with molten NaOH in it appeared to have suffered no massive effects, just some slight rusting.

But what I have done is not the important part, it's what I've learned.



  1. Current density is everything, therefor both electrodes should be short and posses relatively little surface area.
  2. Cast iron is resistant to NaOH to a suprising degree.
  3. A torch is not a good item with which to heat large quantities of NaOH.
  4. Constantly burning the H2 coming off with a constant running torch rather then allowing it to accumulate and ignite for sodium laying around is a good idea.
  5. Insulation around the cell is a good idea, as is a lid.
  6. Wood chars easily from the heat of a Castner cell and can start fires.


What I would consider to be a good vessel now. A reducing adapter for pipes, preferably with the largest differential. Then a plug at the bottom. Electrodes come in from the sides and almost touch in the center at the bottom of the vessel. In the center just below the surface across the top should be a sheet of stainless steel. Na accumulates on one side, O2 goes off on the other. So much simpler then my design.

I tried to draw some of this up but I'm terrible at using computer drawing programs.

Overall the experience was not bad at all, until I realized that the extra hot NaOH would attack me so readily.

rainedout.jpg - 63kB

vulture - 16-8-2004 at 04:06

I'd love to be your neighbor! :D

BromicAcid - 16-8-2004 at 19:29

Thanks Vulture, and I bet my neighbor would not mind in the slightest swapping places with you! ;)

I'm doing better today. The NaOH fumes and burning Na really messed with my eyes, don't know why I wasn't wearing goggles. They're all bloodshot now. Also where I got NaOH (l) on my arms.... It looks bad but it was only in small spatters, as I told my girlfriend "It's like I got liquid delete key splashed on me."

Castner Cell V 3.0 is almost 75% completed (although it no longer looks like a Castner Cell) I've got high hopes for it to continue my trend:

V 1.0 Cost about $90 and produced 0 g of Na
V 2.0 Cost about $30 and produced about 3 g Na
V 3.0 has a projected cost of $10 and should therefore produce >3g Na, right?

Actually this one is shaping up to be a good one. But what I really need is a diaphragm, which is hard to come across, the best material that I have come across is woven graphite thread which you can buy in large sheets for welding protection. But it's expensive and I don't need a large sheet, I guess I can do without...

I've made some hand drawings of my past cell and this one and I'm taking pictures of this one taken apart. Will post tomorrow or the next day.

rift valley - 17-8-2004 at 06:53

Can't wait to see V 3.0! What are you using as a power source a car battery?

Sodium Cell V 3.0

BromicAcid - 22-8-2004 at 14:19



My setup for this is picture in frames 1 and 2, it is made from pipe fittings. In English measurements I have a 2 in. to 1 1/2 in. reducing adapter screwed into a 1 1/2 in. to 1/2 in. brushing. This makes the body of the cell. A 1/2 in. plug was bought to fit into the brushing and two holes were drilled at the extreme sides of the plug to accommodate two nickel electrodes.

One electrode was inserted to expose 1.6 cm into the melt and the other inserted to expose 1.2 cm to the melt, this resulted in a calculated current density of 3.51 A/cm2 for the larger electrode and 5.0 A/cm2 for the smaller electrode assuming amperature of 15 which is the Max my battery charger could get to. However the maximum current during the experiment was around 10 A therefore these numbers must be adjusted. The electrodes were spaced roughly 1 cm apart.

They were held in place and the plug was filled with a two part moldable putty advertised as a steel welding compound. It holds up reasonably to the temperatures and extreme conditions associated with this experiment plus it is non-condutive. As you can see in picture two this whole plug was able to be separated (although the electrodes are fixed if the current is too low NaCl can be added in a small amount, this greatly increases the conductivity of the cell, however it supposedly increases cell corrosion on a comparable level, the latter I have not noticed).

In picture one you see the divider I have in the cell. This was a tight fitting piece of sheet nickel that did not extend between the electrodes, stopping just short of them. This was so as the sodium rose to the surface it would stay away from the oxygen rising right next to it. It worked very well for this purpose and the two sides of the cell showed different corrosion afterward as a result of it.

Initially 15 - 20 ml of pre-molten hydroxide was poured into the cell and the current started immediately. However before I could get more NaOH melted (I chose not to heat the cell directly, relying on resistance heating to do the job) the sodium production, which began very rapidly blew all the NaOH out from between the electrodes and solidified the melt after rendering the condutive component ineffective.

It was my mistake that I attempted to add more molten NaOH to this directly as it did not melt the NaOH coating on the electrodes and therefore I was left with a centimeter of NaOH solid over my electrodes. In an emergency pinch I put some water into the mix and put two new electrodes in from the top, from here I used resistance heating to melt my way to the electrodes ( I also added a few pellets of KOH, this shows a definite increase in melting speed from eccentric formation but overall potassium yield is low), which took quite some time, but finally I was able to hook the imbedded electrodes back up and begin again.

The top of the melt kept solidifying and I had to break though the crust to get to the sodium below. In picture 4 you can see my stirring rod lifted from the melt, shiny blobs of sodium clinging to it. All in all I had a small collection of sodium, about 1 gram, however much more was created but did not get collected for various reasons.

This cell wins my certification for what could be the best medium production cell I have encountered. The most major problem being the electrodes were too close together, this resulted in the sodium forming occasionally shorting out the cell, and localized overheating which eventually nearly lead to the metalloid compound that thwarts some cells. Therefore I would increase the size of the bottom brushing and in turn increase the distance between the electrodes by nearly one centimeter.

Also some outside heating should be available, an electric coil would be ideal, that lacking insulation would do the trick. Better division of the compartments is not necessary but a lid, as shown in the picture is, not to keep gasses out but to eliminate spray from the electrode gasses rising to the surface.

I might experiment with sodium production more but I believe this is the pentacle of my abilities, it is cheap, easy to produce, and you could buy and endcap for the other side to cap it up when not in use for a constant sodium production apparatus.

P.S. Rift, my power source is a car battery charger.

Tacho - 25-8-2004 at 08:36

Funny...

This is a great work and nobody is posting any answers to it! Few months ago people just couldn't get enough of sodium...

I have been terrible busy lately and can't make long posts, but I'm very impressed Bromic, this is THE easy way of making electrochemical sodium!

I would like to know what is that septum made of and what prevents oxidation of sodium once it floats. You probably explained it in your posts, and I will read them more carefully when I have more time.

That work deserves to be better documented! Could you make more pictures available?

Anyway, congratulations!

chemoleo - 25-8-2004 at 11:38

Bromic, is it possible you draw a simple diagram of the cell? I somehow have trouble figuring where the putty, and the different steel parts are.
Also - the top of the cell - is it covered? If so, by what?
And please remind me - how does your system avoid making this grey NaOH/Na mixture? I.e. how come solid Na can be taken off under the NaOH crust? Mmh I think I asked something similar once - but I fail to remember the answer.
Anyway, great job!
So in essence, the whole job could be made to run continuously if a weak outside heating source was applied?

vulture - 25-8-2004 at 13:20

Quote:

This is a great work and nobody is posting any answers to it! Few months ago people just couldn't get enough of sodium...


1) We're jealous.
2) We wouldn't want to spoil such a masterpiece with our insignificant replies.
3) Sodium - Heat - Flames - Apparatus - You can't possibly pump up the drool factor anymore!

I'd like to see a drawing of the cell too, because this is something I tend to pursue in the coming weeks once I get my nickel crucible.

BromicAcid - 25-8-2004 at 20:01


I tried to draw this as well as I could, but I'm still not too good at drawing, hopefully, this combined with the pictures of the real thing above should give a thorough idea of what this thing looks like. [Note: NOT TO SCALE]



  1. This is a reducing adapter, it reduces one pipe size to another, the top opening which is the opening to the cell is 2 in. and it reduces to 1.5 inches at the bottom opening. It is threaded at the top and bottom. On the inside it just slopes down gradually after an inch or two. It is stainless steel.
  2. This is called a brushing. It does the same thing as the reducing adapter but less gradually. It basically acts as a total plug but with an opening of the desired size. This brushing fit the 1.5 inch opening in the reducing adapter (A) and left an opening in the bottom of .5 inches. for the plug (C) to fit into. This is threaded to screw into the bottom of the reducing adapter, and the hole in it is threaded as well for the plug.
  3. This is the plug. It fits the hole in the brushing. What it is normally is simply a plug, there is no way for liquid to escape and it is for sealing off extra outlets in pipework and such. But in this one I drilled two holes to accommodate the electrodes, you can see this removed with the electrodes inserted in it, in the post that I did above.
  4. This was the anode, made of nickel. Both the cathode and anode were made from wire of the same length and not cut down. The anode went into the mix deeper because current density on the anode is less important, plus I wanted to make sure there was enough conductive area inside to allow for that much current transfer.
  5. This was the cathode. Small amount was exposed to the inside of the cell to achieve a high current density (5.0 Amp/cm2) which is significantly higher then the current density mentioned by Organikum at the beginning of this thread. Notice how I had the portion of the anode and cathode at the bottom of the cell different lengths sticking out, this was so I could differentiate between them once the cell was running because it all looks the same from above.
  6. This is where the putty went, it came up to be even with the bottom of the brushing adapter. It stopped current from traveling between the electrodes too low and insulated them from shorting out with the inside of the cell. As I said before this was some kind of 'cold weld' mix that came in a roll, you cut off a piece and manipulated it till it was of a homogenous consistency then applied it and it hardened rapidly. Not recommended for this environment but it held up.
  7. Part G is a piece of nickel plate. It was jammed into the cell to divide it in half. Notice how the electrodes are on either side of it, and the divider does not dip between them. This was just so sodium formed, rising up would not encounter much oxygen doing the same because less then 1 cm past the electrodes the rising elements were divided.


All the parts where put together without any sort of sealant, just used a pipe wrench. The divider need not be nickel, the electrodes don't have to be nickel either. The electrodes do not have to in that manner, the basic design is there.

This was not the perfected cell as I said before, but it has the ability to be nearly perfect for a middle sodium production level. The loop method actually seems nicer for lower quantity sodium. What my problem was, was the spacing of the electrodes, they did not seem to enter the molten salt far enough as my current didn't rise much above 10 amp, and they were too close, the solution stayed very molten in the bottom but the top was solid, which brings me to my second problem, external heating must be applied to the top.

If the electrodes are too close you can get a hot spot that can cause the metalloid to form, too far away and electrolysis becomes difficult. In my setup here they were very close, too close as my final conclusion. But other then that it worked really well.

The lid for the cell can be anything, I just set it on there to prevent the spray of molten hydroxide that comes up during electrolysis, and partially to keep the hydrogen coating over my molten sodium. All I used was a sheet of metal that did not even cover the top entirely. But it would be nice to have a plug for the top too since it is already threaded, easy storage and easy to render 'safe' should an emergency arise, just remember to turn off the electrolysis first.

I never got a good method to get the molten Na out though, I used a little scoop I made like a ladle but it was not good, brought over hydroxide, probably introduced impurities, hard to get the Na out. I personally wanted to try an eye dropper in preheated mineral oil, before taking sodium out sucking up some mineral oil to heat the dropper and pushing it back out, then using the dropper to suck up the sodium.

I put the electrodes at the bottom for two reasons, A) I couldn't find a good diaphragm to separated them that was not metal and I didn't want risk shorting the cell out. When the electrodes were at the bottom I could put the separation right above and it worked. B) When the electrodes come from the bottom there is lots of working room above the mix, you are not trying to avoid bumping electrodes and such.

Quote:
So in essence, the whole job could be made to run continuously if a weak outside heating source was applied?


That was my goal to all of this. Simple sodium generation when necessary for however long is necessary from common materials. As with any Castner cell though the problem of long running is the side reactions producing sodium oxide which slows and eventually stops the cell. I believe this could be avoided if when the cell starts to loose electrolyte you just replace it with NaOH. Commercial NaOH contains excess H2O usually which has to be electrolyzed out first and boiled out, if the cell were turned off and NaOH added with H2O as a contaminate, you will hydrolyze your sodium oxides formed and therefore refresh the ability of your cell to run.

Quote:
And please remind me - how does your system avoid making this grey NaOH/Na mixture? I.e. how come solid Na can be taken off under the NaOHcrust?


Now that I've made the grey mixture I have a better grasp of it. If your electrodes are too close, localized high heating, therefore grey mixture forms, and it spreads and eliminates the constructive conductivity of the cell. As I've said, the electrode spacing is the most important part especially since the electrodes are immobile. Too close and you get overheating, sodium coming between the electrodes and shorting them out, and possible NaOH/Na mix formation. Too far and the actual work performed drops and the electrolysis is sluggish. The Na formed under the electrolyte, rose to the top, and collected under the hardened crust, when I broke the crust the liquid Na collected on my stirring rod (a nickel wire) and I took the picture.

Steels of all sorts have decent resistance to NaOH, copper is attacked rapidly by slightly wet NaOH when heated, haven't tried it in anhydrous. NaOH fresh from the molten mix on a stirring rod reacts quite violently with water (no surprise). If you have a stirring rod of sorts get some pliers to break off the NaOH that makes unwieldily coatings on it though usage.

I will answer more questions as they come ;)

Great job!

chemoleo - 25-8-2004 at 21:03

Great job on the diagram, I think this is what we all needed!
I do have a few questions though:)

For one thing, how do you avoid the electrodes from shortcutting through the plug C? I guess plug C is made of metal right? In that case presumably the holes through which the electrodes are threaded are greater than the diameter of the electrodes, and the insulation is provided by the 'putty'? In that case, what is this mysterial putty made of that it resists molten 310 deg C hot NaOH (and is an insulator too, at those temps?)?

Regarding the grey NaOH/Na mix - this is the SOLUTION to a great problem! Everytime I tried making Na, I had this particular problem. How certain are you that the temperature is the cause of this problem? I.e. you wouldnt possibly be able to take the temperature between the electrodes? If temperature is such a crucial factor to this - then I wonder how they got it done in the original Castner Tiegel description.
The only way I can see the whole temperature issue to work out (without major investment in equipment) is to provide for decent insulation. I was thinking along the lines of resting the whole cell in a Al2O3/SiO2 putty, with a few Kanthal wires inside. The Al2O3/SiO2 would then serve as an 1) insulating material, 2) which is heat resistant and shows no great thermal expansion coefficients 3) also an electrical heating mantle. I guess then power could be applied to the heating wires within, and the optimum power would have to be determined simply by trial and error. But once established - Na production would run at the max!

Also, I was thinking about the separation of the electrodes. O2 and H2 interfere with the reaction, so there needs to be a decent separation between cathode and anode, as you have done with Ni-plate G. Great idea btw. I wonder where u get all that nickel from. Anyway - is there a chance to shape this into some Y shape - i.e. to ensure even greater separation of the gases? Or - even better - to have a relatively small exit hole (i.e. 2 cm diameter) for each electrode, so that 1) heat loss would be avoided, and this problem of crust formation and 2) to increase separation of the gases forming at the electrodes? Of course, then this would have to be a removable device, else the Na couldnt be taken off.

Generally I am not such a great fan of the idea of taking off Na every few minutes/tens of minutes. Dont you think it would be neater to have the Na accumulate to a certain extent (i.e. 10s of grams worth), then to take it out, add more NaOH, and continue? I mean - what I don't like about this is that it reminds me too much of the loop method - where one gets a scoop of Na every few minutes which weighs a small fraction of a gram. Surely this can be improved?

Anyway - great job once again - you are on the path to eternal Na-fication!

[Edited on 26-8-2004 by chemoleo]

BromicAcid - 26-8-2004 at 15:07

Quote:
In that case, what is this mysterial putty made of that it resists molten 310 deg C hot NaOH (and is an insulator too, at those temps?)?


Steel Epoxy Putty by Devcon, 'Leak Stopper' It is two parts, it looks like a roll of clay and there is an inner color and an outer color, you kneed the two until uniform consistency then press into place. It insulates the electrodes from one another very well, but it's resistance is not so great, it gets pitted and such but it is replaceable. The package says that it works to 200 F but it works well beyond that for my purpose, it gets brittle at this temp but because it is a solid plug not subjet to mechanical strain it holds up beyond this. It advertises itself as chemically resitant. Another thing I experimented with was fireplace moarter, it comes in a caulk tube for a caulk gun, problem is you have to apply it in thin segments because heating is necessary between to cure it. Also it dissolves even more so in the molten hydroxide, I guess the sodium silicate, the main ingredient is soluble in the hydroxide melt.

Quote:
How certain are you that the temperature is the cause of this problem? I.e. you wouldnt possibly be able to take the temperature between the electrodes? If temperature is such a crucial factor to this - then I wonder how they got it done in the original Castner Tiegel description.


The original Castner cells were designed much bigger with a larger gap between the electrodes and different spacing, i.e., multiple anodes and such. In this version it is hard to maintain the current density if the electrodes are spaced far apart with conventional equipment, therefor they have to be close and you get hot spots. In the industrial cell with the electrodes spaced the way they were the heat could dissipate the temperature of the cell could be assumed to be roughly equal everywhere. However on our scale this is not one of our luxuries.

Quote:
Anyway - is there a chance to shape this into some Y shape - i.e. to ensure even greater separation of the gases?


What do you mean shape it into a Y, how?

Quote:
Generally I am not such a great fan of the idea of taking off Na every few minutes/tens of minutes. Dont you think it would be neater to have the Na accumulate to a certain extent (i.e. 10s of grams worth), then to take it out, add more NaOH, and continue?


Well, if the partition separating the two halves does a good job at the top the Na can accumulate on the one side there. It would be protected under the hydrogen atmosphere identical to how it is in a Castner cell, then you could let it run for 30 minutes or so and ladle it out. That is once you get the electrode spacing correct, mine were too close, I bought a new end plug today to reset the electrodes, same distance into the melt, but another centimeter or two apart, this should also afford better separation of gasses.

I think that I will set the whole upper half of the cell in plaster today or tomorrow, good idea, nice insulator, put some heating elements in there if I can find any, if not, well, I'll work around it.

Edit: Took the whole cell, wrapped it in a heating coil for an electric stove with a variable control switch, imbedded it in plaster of Paris.

[Edited on 8/27/2004 by BromicAcid]

rift valley - 27-8-2004 at 15:43

Quote:
Originally posted by chemoleo


For one thing, how do you avoid the electrodes from shortcutting through the plug C? I guess plug C is made of metal right? In that case presumably the holes through which the electrodes are threaded are greater than the diameter of the electrodes, and the insulation is provided by the 'putty'?


I am also curious, as i am making a cell off of your design I already have all of the parts. So how do you keep the electrodes from shorting out when you pass them through a metal cap?

Cyrus - 27-8-2004 at 18:10

How about using the alumina crucible method you (BromicAcid) suggested to me to make a plug. Also, if sodium silicate (from the dap stuff) is soluble in NaOH, why not just let the NaOH get saturated with sacrificial NaSiO3, and then add the plug. More work I know, and it probably will ruin the reaction, but I CAN'T STAND expendable parts (or planned obsolesence. )

I'll test the alumina ceramic's resistance to NaOH today or soon.

BromicAcid - 27-8-2004 at 19:42

The holes drilled in the cap are significantly larger then the diameter of the electrodes. I packed the steel epoxy mix around them and filled the depression in the plug, this insulated it.

Another possible way that I was considering is a play off of the original method. Imagine my current cell except in place of the brushing and the smaller plug there was just one large plug at the end. Into this was drilled two holes to accommodate the smallest diameter pipe one could find. They would be drilled across from one another then the electrodes inserted into them. Then before running molten NaOH would be poured into the pipes to insulated them further down as it cooled.

That is similar to how the cathode is insulated from shorting out in the original Castner cell. You couldn't put the two electrodes next to one another in the same pipe and insulate with NaOH because as the electrolysis progressed it would heat and melt its way straight to the bottom of the electrodes.

vulture - 28-8-2004 at 02:18

Unless you're alumina is pure korund, eg the sintered and extremely unreactive version of Al2O3, it's going to dissolve in NaOH over time.

vulture - 28-8-2004 at 12:42

Tonight I've been flicking together a cell myself.

The pictures should speak for themselves.

The idea is to collect the sodium formed at the cathode inside the pipe to reduce loss. There is a problem however; the pipe is made of galvanized steel. :( Now I know this isn't ideal and that it's probably going to shortcut the cell when the molten sodium collects in it, but at the moment I have nothing better at my disposal.

I'm planning to use thick copper wire both as anode and cathode material.







The outside ring of insulation is mainly to keep (possible) combustion heat from reaching the electrodes and such.

I'm going to test it without the electrodes but with the pipe as soon as the weather clears up (blasted belgian weather!!!) to see if it can actually melt NaOH and how the pipe will react.

EDIT: The vessel is a tobacco can. It's very similar material as a soupcan. We'll see if it holds up.

EDIT2: Bugger. The resistance between the inner and outer wall of the pipe is 0,4 Ohms at roomtemp. I wonder if passivation in HNO3 could solve this.

I'll be using an old ATX power supply that delivers 18A @ 5V.






[Edited on 28-8-2004 by vulture]

vulture - 29-8-2004 at 04:01

I've put the apparatus on an electrical hotplate (500W) without the electrodes, just to see if I can reach the required temperature. Currently the temperature on the outside of the can, approx halfway the apparatus is 305C. I still have a few other problems to solve, like inserting the electrodes, because the NaOH formed a rather hard crust.

I've exchanged the cathode holder by a piece of insulating material.

The main conclusion of this test is: insulation is everything

I got stuck somewhere around 250C with the setup like it was in the previous pics.




EDIT: Scrap that, temperature is currently 324C...:D There are some transparent spots developing in the NaOH too...:D

EDIT3: Ok, sofar the weather is holding out.
The NaOH melted to a black mass, possibly because of contamination from the can.
Let's see how the steel pipe holds up in there...



[Edited on 29-8-2004 by vulture]

BromicAcid - 1-9-2004 at 15:54

You know that putty that I keep going on about... turns out then when the NaOH is hot and a lot of the surface area of it is exposed... well... let's just say it's not so resistant any more.

Just a warning.

Although I found out that a stove heating coil for a hot plate with the resister switch in place circled around my previous vessel will keep it liquid on its own. Plaster of pairs steams a lot when it is used to keep the vessel insulated but it eventually stops and works great.

vulture - 2-9-2004 at 01:13

Some testing yesterday with the steel pipe in the setup was rather dissapointing, the pipe seems to cause huge heatloss, I couldn't get above 266C. Alas, I borrowed my fathers hot air gun and activated it at 530C :D.

Twenty seconds...hehe...:D

The only problem I have now is that I keep shortcutting my electrodes either way through the can or by touching the pipe. And the ATX power supply has a rather sensitive shortcut sensor, cuts off immediatly.

Does CuO dissolve in hot NaOH? I have copper pipe which would be ideal, if I oxidize the outside to CuO I could prevent nasty shortcuts and sodium forming on the outside.

vulture - 3-9-2004 at 00:36

Some further observations...

I've been using a copper pipe now instead of the galvanized steel one. It is oxidized by the heat but immediatly reduced back to pure Cu when electrolysis starts.

Furthermore, the electrodes should be seperated atleast 2cm if the current rises above 2A. My run when they were to close resulted in something that could best be described as a piece of artillery...
BANG[pause]BANG[pause]BANG[pause] etc which was quite nerve wrecking.

Despite the electrolysis was barely enough to keep the NaOH molten I still end up with the grey stuff. :(

[Edited on 3-9-2004 by vulture]

rift valley - 3-9-2004 at 04:10

today I am going to try it with my variation of bromic's cell. I purchased a 10 dollar water heater for the heat source but I cracked the metal pipe the contains the heating wire and some dust like material (do you guys know what that stuff was?) Since my power source blows I an going to heat it additionally with a propane torch. I'll let you guys know how it turns out!

vulture - 3-9-2004 at 07:40

Don't heat with a propane torch, the CO2 will react with your NaOH.

axehandle - 3-9-2004 at 07:55

Quote:

...some dust like material (do you guys know what that stuff was?)

Something ceramic probably, heating coils are usually embedded in ceramics. If you cracked open the heater to get to the coil, why didn't you just make your own coil in the first place? *confused*

TheBear - 21-10-2004 at 11:28

Success. I managed to make myself some drops of sodium using the wire slope setup. However I found out that the NaOH solidifies to fast using such small quantities and stainless steel eggcup.

By the way. Corrosion was massive and rendered the dark but clear NaOH a brown "mush". Stainless steel was used both as cathode and anode. (Cathode was made out of "steelwire" and it didn't seem to be zinkplated, I guess this is stainlesS?). Anyways, the anode (stainless eggcup) was heavily corroded and a yellow salt was formed on it's side above the NaOH surface.

I found out that the intense gas release ejected the formed droplets of Na in my slope which made extraction very hard. And further on I can tell you that sewing-machine oil is not inert to Na. :(

Need to get myself some charcoal lighter fluid. Thanks everyone for giving me the inspiration and providing information. I'll be getting back to this experiment in the near future.

vulture - 3-4-2005 at 03:37

I've tried it again, this time with a nickle crucible and steel electrodes. NaOH melted very easily, seems Ni has a rather good heat conduction.

Electrolysis went smooth with lots of little globules and lots of corrosive vapor.

The only problem is that I now have a large black mass of NaOH/Na which is rock hard and I don't want to wreck my crucible.

I don't think melting under xylene will work as there's a massive layer of crystallized NaOH above it.

BromicAcid - 3-4-2005 at 11:49

That's a toughie.

Maybe add another salt to it when molten to decrease the solubility of the NaOH. Maybe melt under rock oil. Maybe try to heat and remove liquid Na. Nothing I can think of sounds pleasent.

BTW, I kept my 2 kg lump of NaOH I got from my Castner cell run and I use it for things like making aqueous NaOH solutions to neutralize chlorine and bromine and such. I tossed a piece into some water the other day and it turns out it was hiding a small piece of sodium which quickly made its way to the top and bursted into flames.

fishy1 - 30-4-2005 at 13:57

would any of these battery chargers work?
http://www.argos.co.uk/webapp/wcs/stores/servlet/ArgosBrowse...

Organikum - 30-4-2005 at 14:43

Quote:

and some dust like material

Magnesium oxide.

fishy1 - 2-5-2005 at 13:31

will either nichrome wire or copper wire react with NaOH?

12AX7 - 2-5-2005 at 17:25

Nichrome might (as I recall, most chrome alloys are protected by a layer of chromium oxide), copper shouldn't. Copper also tends not to react with acids either, at least very quickly.

Tim

BromicAcid - 23-5-2005 at 12:53

THE RATE OF DISSOCIATION OF PERCHLORATE ION IN FUSED SODIUM HYDROXIDE

1,2 Ralph P. Seward, Harry W. Otto;
J. Phys. Chem.; 1961; 65(11); 2078-2081.

Quote:
Aluminum containers were used for the sodium hydroxide fusions in this work. When aluminum is immersed in fused sodium hydroxide, gas evolution from the surface of the metal occurs but this lasts
only a few seconds. It is proposed that the protective coating consists of a layer of an insoluble sodium aluminate since if the metal is removed, washed and then returned to the melt, the brief attack occurs again. While nickel is satisfactory in resistance to corrosion by fused sodium hydroxide at moderate temperatures, the unfortunate tendency of the liquid to creep up the walls of the container, to solidify when it reaches a cooler spot, is much more noticeable in nickel than in aluminum. Corrosion of the aluminum containers did occur but slowly enough so that they could be used for many hours with only a few milligrams loss in weight.
Yes... I may have guessed that aluminum may form a passive coating against molten NaOH, however I would have never truly expected it.

garage chemist - 23-5-2005 at 15:13

Some time ago, I prepared several grams of sodium with the soup can method.
I melted approx. 200g NaOH in an old soup can (previously heated with bunsen burner to burn off the plastic coating on the inside) and connected the can to the positive pole of a laboratory power supply (5 Amps at about 12V- more current would be better).
The NaOH was melted (just melted- NOT heated further, this is very important!) and an iron wire, connected to the negative pole, was inserted about 1cm into the melt.
When the temperature is right, the Na collects as a single globule which is attached to the wire and floats on the NaOH. It grows bigger and bigger and then seperates from the wire and swims around. It is taken out with a previously heated spatula and immediately tossed into a small beaker filled with low viscosity paraffin oil (or xylene or BBQ lighter or whatever you prefer).

The temperature of the molten NaOH is VERY critical, only 10°C too hot and the sodium will simply dissolve in the NaOH to form a black conducting metalloid from which no sodium can be isolated. The heating should be very gentle and some solid NaOH should be present at the sides of the can. The NaOH should be as close at its solidifying point as possible.

This process is repeated several times and the paraffin is then heated until the sodium liquefies. The Na drops are melted together by gently stirring them with a bent piece of strong wire (this is not as easy as it sounds, but it can be accomplished). Bits of NaOH are removed by poking the liquid Na and removing the solid pieces.
By this method, one can collect about 5g of quite pure sodium a day, depending on the current and temperature.
There's no need for huge amounts of NaOH or special apparatus. Only a soup can, a good power source, some strong wire and patience are required.

I use my sodium mainly for drying organic solvents, only very small amounts are needed. 5g of sodium last a long time.

[Edited on 23-5-2005 by garage chemist]

garage chemist - 23-5-2005 at 15:22

A pic of my entire setup (I used a computer PSU the 12V line was used- with 5V, not enough current was flowing).

[Edited on 30-1-2007 by chemoleo]

Img_0037.jpg - 54kB

garage chemist - 23-5-2005 at 15:24

The molten NaOH

[Edited on 30-1-2007 by chemoleo]

Img_0038.jpg - 85kB

garage chemist - 23-5-2005 at 15:27

The sodium pieces under paraffin, prior to melting.

I have no pics of the actual process, sorry.
I have some videos of the process (and melting together the Na, plus a video where the Na reacts with water, it caught fire), but they are way too big to upload.

[Edited on 30-1-2007 by chemoleo]

Img_0043.jpg - 46kB

my own Downs cell

tumadre - 2-6-2005 at 12:01

I am constructing my own Downs cell, The general construction is an "oven" consisting of the 1/4 inch thick steel rectangular trough 8" by 4" by 6" tall, (outside dimensions), and at the temp of 873K this radiates 4700 watts (black body temp). This trough is wrapped in ¼” asbestos.
The heating element is a bicycle chain in a coil insulated electrically from the steel by thin strips of asbestos. The dimensions of all this were chosen carefully so that all this could be surrounded by one layer of firebrick. This firebrick is surrounded in fiberglass and sheet metal, (to keep the atmosphere from entering this chamber) and is then surrounded by the 4” by 4” by 8” cement brick. The overall dimensions of this are about 2.5 feet cubed. I currently have no method of attaching photos.

My question is this, what ceramic will withstand a 575-585 C solution of nacl and cacl2, the ceramic is necessary to separate the steel trough (the cathode) from the graphite anode sitting in the center.
Second, will the calcium precipitate out from the liquid sodium and settle back into the bath where it dissolves in the molten salts or will it react with nacl and become Cacl2, thus requiring only the addition of Nacl?
My power source for the electrolysis is a 900-watt transformer that I completely made myself from two sets of E cores that I removed from two home backup DC to AC supplies. It can produce 4.5 vac at 200 amps or 9 vac at 100 amps, this is then rectified to dc. The steel bicycle chain draws 60 amps at 120 volts (I power this though a triac)
The Idea is to have the sodium run out a pipe into a one-gallon can full of oil. The shielding gas will be CO2 blown though another pipe into the trough, thus the CL2 will be blown out the top, I have the nastiest idea to collect the CL2 and compress it into a can at about 200 psi, at which the O2 N2 and CO2 can be released and the liquid CL2 will remain in the can. Will the sodium that will float on the Nacl Cacl mix be a mix of Ca and Na that will solidify in the runoff pipe? Or will the Ca sufficiently react with the Nacl and thus not be present in the floating sodium?
Most of the physical construction is complete, I have yet to get the steel welded together and the heat turned on full, I have proved that 2000 watts is all that is necessary to keep everything at 600C based on calculations at reduced power.

12AX7 - 2-6-2005 at 15:26

Wow, sounds neato :D

Calcium is insoluble, heavier and has a higher melting point than sodium, and more than the electrolyte hopefully (hence using enough CaCl2 for the low melting point eutectic). It also has a somewhat more negative reduction potential than sodium, so it probably does react to produce sodium metal. Hence the calcium chloride ought to be inert. :)

Tim

BromicAcid - 2-6-2005 at 18:31

I believe that sodium produced in this manner has a calcium precentage of <1% the calcium does indeed crystalize out and fall back into the melt and this does react further with the NaCl there to produce more Na instead of calcium.

As for the ceramic material, alumina and magnesia based ceramics may work, the chlorine being the main culprit of damage here to ceramics so things are somewhere easier then using a castner cell where the melt will eat a number of ceramics and glasses. I had plans for a similar cell on my site but alas I am lazy and haven't started construction. My intention was to just use a high-magnesia pot from my gardening supply and invert it, drilling the hole in the bottom (which would be attached to the top of the lid) and having the carbon anode come through that attached to a copper wire (which would be running through a copper pipe and hanging there).

Anyway, to attach pictures just click the button 'Browse...' next to attachement under the box where you write your posts, this will attach one file of a decent size, multiple files can be attached in multiple posts or you can go to the topic 'Forum Matters' where there is a sticky for using the forum hosting services to upload multiple pictures, from there inserting them in the thread involves remembering the URL for them and clicking the button above showing the little picture of a mountain.

Looking foreward to hearing your results.

Cyrus - 3-6-2005 at 09:57

Wow, tumadre, that's a huge container for sodium production!

Are you sure you need that much insulation? (I suppose you've calculated everthing out, and I haven't, but it does seem like a lot of insulation. Have you looked into using kaowool insulation?)

Hmm, ceramics that resist chlorine. I don't know... what would the reaction be? BromicAcid, why are MgO or Al2O3 containing ceramics best here? (just curious as usual) I did a bit of googling on chlorine and ceramics, but never found anything. Molten NaCl/CaCl2 shouldn't be a problem at 550 deg. C. or whatever it was, but it will leak through porous ceramics noticably. :(

I still want to do this reaction too, as soon as I get a good power supply. I suppose I could rig up something using the MOT I got. As for heating it, sticking the apparatus inside of a furnace would work, although it wouldn't be too precise. But I don't think NaCl electrolysis is as sensitive to changes in temperature as NaOH is.

Molten NaOH in an ALUMINUM container!!! :o:o Now that's confusing, especially because of the thermite reactions that occur with lye and aluminum. (Tacho was doing experiments with these)

"Ceramics uneffected by chlorine"

Natures Natrium - 3-6-2005 at 11:59

According to patent US 1,926,072, (quoted elsewhere on this board for the production of PCl3), an alundum (aka alumina) boat was capable of withstanding an atmosphere of chlorine at >900C, even in the presence of finely powdered carbon.

[Edited on 3-6-2005 by Natures Natrium]

12AX7 - 3-6-2005 at 12:08

The problem with ceramics is they are slightly soluble in NaCl. Al2O3 you may note is soluble to several percent in fluoride melts. Chlorides aren't as good, but it's still there. This would react with the sodium, calcium and electricity to form aluminum and silicon.

Metal is demanded. Stainless might work, Cr2O3 probably isn't very soluble in chloride. A copper vessel could be held in a reducing atmosphere, though it still readily reacts with chlorine gas.

Oh, the phase diagram for Ca-Na shows, at most, 1.5%at solubility. It is dramatically lower at lower temperatures, 99.95% or so should be had on cooling to 100-150°C and filtering the calcium.

Tim

tumadre - 3-6-2005 at 12:55

I know it’s big but the cost of Nacl is $3.12 for 25 pounds, and I have many uses for sodium, 100 amps will make about 1/5 pound per hour. at 7 cents per kilowatt hour electerical cost, this makes about $1.50 per pound.
The ceramic is the divider; it is necessary to prevent the sodium from touching the carbon anode. I bought 25 pounds of standard white clay from my high school art class ($7), I am going to fire a sample of it and let it sit in a container of liquid Nacl and Cacl2 to see what happens.

BromicAcid - 3-6-2005 at 13:14

How are you going to keep the melt at the proper composition of CaCl<sub>2</sub>/NaCl ? For my plan I was just going to use a mixture rich in NaCl and melting at a higher temperature and keep the electrolysis proceeding until the temperature to keep the mixture molten was exceeded (so the NaCl concentration would decline to the eucetic of the mixture then continue to decline during which time the melting point would rise) so are you going to have some sort of feeding system for adding NaCl during the electrolysis?

tumadre - 3-6-2005 at 13:34

If the Cacl2 remains the same, them only by adding too much Nacl will there be a problem. I have not yet constructed the steel and pipes so I have not designed the Nacl insertion apparatus

12AX7 - 3-6-2005 at 18:05

Ya know, if you keep it just above the eutectic temperature, you have three conditions:
sodium-rich: NaCl crystallizes out
neutral: fully molten solution
sodium-lean: CaCl2 crystallizes out

Since sodium content is constantly falling, the only way the first condition can occur is if you add too much. If you add too much, you get a supersaturated solution of NaCl (in CaCl2) and no more will dissolve. If sodium falls too much, CaCl2 will crystallize on the coolest and/or most sodium-deficient surface, which means either the top or bottom corner of the cathode.

The best way to go about this, I think, would be to make (anhydrous!) salt briquettes. You could try making cakes of salt by evaporating water and drying them (heating slowly to a pretty good temperature, I'd say at least 200°C), or perhaps liquid-phase sintering a mixture of mostly NaCl with small amounts of KCl and CaCl2 which form a tertiary eutectic which fuses it together at say 400-500°C. The fusing would guarantee anhydrous conditions, always useful when adding to a very hot solution.

Then to use, just drop them in as needed, let it suck on the ice cubes (so to speak) and if you add too many, so what, the excess of sodium is localized right there, they'll simply dissolve as needed!

Edit: or yeah... you can just melt and cast salt ingots (mind that they are very fragile from such sudden cooling), if you can reach the additional temperature (red/orange heat).

Tim

[Edited on 4-6-2005 by 12AX7]

darkflame89 - 3-6-2005 at 23:31

Would melting sodium hydroxide in aluminium container cause that much problem? Certainly yes if the temperatures were much higher, but at about 300 degrees? Even if reactions were to occur, it would be the fusing of the surface of aluminium in contact with the molten sodium to form sodium aluminate which would form sort of a protective layer, since it melts at extremely high temperatures.

tumadre - 7-6-2005 at 11:37

please read my previous post before answering this question.
Will propane react with the released CL2 in a non explosive manner as methane does? I am comsidering using propane as the shealding gas instead of co2 because three pounds of cl2 every five hours is too much, but 6-10 pounds of HCL and clorofoam is more easly disposed of/ or dissapated into the ...

BromicAcid - 7-6-2005 at 19:59

Of course you wouldn't get chloroform, you'd get CCl4 and other chlorinated but that is a minor point, the reaction of Cl2 with butane is rapid at 30C in the presence of light and the reaction of methane with Cl2 is explosive (if stoichiometric) in the presence of light, but it's hard to initate without light (or so I've been lead to belive) however.... it all depends on the tempreatures involved (which in your case are ~500 - 600C) so I'm at a loss for the specifics but I would say there is at least a noticable danger factor involved.

Why the need for a shielding gas? The Cl2 producing chamber is separated and even if it does react with some of the NaCl it will just electrolyze again. H2 makes a good shielding gas for Na however it would explode from contact with Cl2.

12AX7 - 7-6-2005 at 21:25

I don't think activation energy is a problem, flames are awfully hot.

Does CCl4 decompose with heating? Is HCl preferred?

Tim

[Edited on 8-6-2005 by 12AX7]

BromicAcid - 8-6-2005 at 09:31

Carbon tet is fairly thermally stable, hence its old use in fire extinguishers but there is bound to be some decomposition at these temperatures.

Attached is THE ELECTROLYTIC PREPARATION OF THE AMALGAMS OF THE ALKALI AND ALKALI-EARTH METALS.
G. McP. Smith, H. C. Bennett;
J. Am. Chem. Soc.; 1909; 31(7); 799-806.

Kind of 'Cold Electrochemical Sodium' really but it is an interesting read and there has been somewhat significant intrest in the preparation of sodium amalgams.

[Edited on 6/8/2005 by BromicAcid]

Attachment: alkalimetalamalgams.pdf (566kB)
This file has been downloaded 1436 times


Polverone - 8-6-2005 at 12:36

While browsing through one of the volumes of <i>A Treatise on Chemistry</i> (thanks, S.C. Wack!) I noticed under an entry on potassium that one suggested method for its electrochemical preparation is the electrolysis of fused KCN, by melting it completely, inserting electrodes, waiting for the surface to form a crust of solid KCN as it cools, and then passing current. KCN has a lower melting point than the chloride, and has the advantage that (unlike the hydroxide or chloride) the anode should not suffer attack. Might it work with NaCN as well?

But that actually wasn't the recommended method. The recommended method was to use a mixture of KCl and CaCl2 mixture with control of the heating flame so that the area around the anode remained freely molten to expel chlorine, and the area around the cathode did not. After a period of current passage, the mass of salts would be cooled and broken under liquid hydrocarbon to reveal potassium metal substantially free of calcium. It might be possible to do the same with sodium compounds instead of potassium, and it would certainly be easier to prepare small amounts of sodium if no inert shielding gas needs to be used.

Oxydro - 22-6-2005 at 08:04

I was just browsing the eutectic-finder at http://ras.material.tohoku.ac.jp/~molten/molten_eut_query1.p... and I was wondering, what exactly is the problem with the GaCl3-NaCl mix? MP of 75-25 mixture is 55C -- I would assume that at that point gallium contamination would be a problem, but say at 50/50? what would happen?

12AX7 - 22-6-2005 at 10:38

Gallium has the lower reduction potential, also any sodium formed would react with it.

Tim

Oxydro - 22-6-2005 at 18:02

Pah. I posted without thinking.

Edit: or maybe with thinking backwards. I was leaving for work, so I don't really remember. Anyways obviously only such things as lithium, potassium and calcium can be used, the only higher potentials according to the list I looked at.

[Edited on 23-6-2005 by Oxydro]

Marvin - 23-6-2005 at 08:14

Calcium yes, lithium maybe (you would probably get lithium instead), potassium no (this is a classic ohshititshoulntdothat moment in the making). You cannot electrolyse a molten salt mixture of potassium and sodium to eather metal seperatly. Ive posted the reasons before as well as why try this is particulally dangerous to try.

[Edited on 23-6-2005 by Marvin]

Cyrus - 30-7-2005 at 13:47

Ahh! I typed a long response and the computer ate it. To put it simply, I used patu's method with an ATX 12v power supply, red devil lye, and a copper anode and cathode. I used a propane torch to melt the NaOH around the anode and cathode, and then kept only the center of the NaOH molten during the reaction. This prevents ALL corrosion from the outside container and prevents the sodium from overheating and forming that "grey stuff". If the sodium hydroxide gets too hot, it will just melt more NaOH.

The copper anodes and cathodes held up much better than iron, and although the molten NaOH was turned blue, blue is a beautiful color (much better than a brownish rusty color), and it didn't seem to affect anything.

There was splattering and popping, mostly at the beginning, after the loop on the cathode was mostly submerged, the popping was almost gone. I got a few miniscule splats of NaOH on my gloves and arms (and face shield) but only one really hurt. It took off a few mm of skin in as many seconds.

I really recommend this method to make a bit of sodium- it's easy, inexpensive, and really pretty safe. Sure, you can get a tiny bit of NaOH on you, but the reaction is very slow and controllable and so there's no danger of any deflagrations or anything spewing flaming mineral oil onto people's heads...

Here's a diagram.

Cyrus

[Edited on 30-7-2005 by Cyrus]

SODIUM!.bmp - 769kB

"Liver of sulfur"

12AX7 - 19-8-2005 at 23:21

Has anyone tried electrolyzing Na2S? Chatting with someone and mentioned its low MP...

Tim

darkflame89 - 20-8-2005 at 01:47

Low m.p. ?

Hardly, checking up its melting point via google reveals that it has a melting point of about 1000 degrees C, decomposing at that point.

The low "melting point" comes from the sodium sulfide monohydrate, having 50 degrees C. Beyond this, and the salt dehydrates.

12AX7 - 20-8-2005 at 18:45

Ah. I'll have to slap my contact then :D

Tim

i am still here!

tumadre - 4-9-2005 at 23:22

It has been a while, but this time I think I have the answer to this eight page question
sodium tetracloroaluminate.NaAlCl4.
It has a mp of just 151 C.
All I know about it is that it was first developted for liquid sodium-zinc and/or sodium-sulfur batterys, so why not just "charge the battery and continualy draw off the sodium and add more NaCl or other sodium salts?

neutrino - 5-9-2005 at 02:56

That sounds like a hard substance to get. Anhydrous aluminum ions are tricky to make.

BromicAcid - 5-9-2005 at 08:07

Even if it is made it does not guarentee any properties that would be condutive to electrolysis, namely conductivity, anhydrous aluminum halides are non-conductive, and although the sodium chloride makes itself into this compound, it may possess more covalent character then would allow for electrolysis, its presence in these batteries being more as an overall solvent or what is being electrolyzed rather then something that can be individually attacked with current to give sodium metal.

But it might be worth a shot, add NaCl to anhydrous AlCl3 probably right?

12AX7 - 5-9-2005 at 08:25

If nothing else, if you assume it as AlCl3 in solution of molten NaCl, any Na formed will reduce the Al, forming Al metal, which I'm assuming is your goal. If kinda inappropriate for this thead...

So yeah you can't make an NaX eutectic with anything but alkali and alkaline earth salts with a higher reduction potential, namely, Li, K, Rb, Cs, Ca, Sr and Ba.

Hmm, most of those aren't that hard to come by. A quaternary or pentanary eutectic between Li, Na, K, Ca, Sr and Ba may melt as low as 200C. :)

Tim

Marvin - 12-10-2005 at 02:08

Mixtures of sodium and potassium salts bring the mp down spectaculally, but on electrolysis alloys are produced that are rather dangerous. You cannot produce pure sodium or potassium metal from a mixture of the salts.

Sodium sulphide has a very high melting point, but it and sodium hydroxide have a eutectic thats a little lower than pure hydroxide, this has been patented but I dont have the details.

neutrino - 23-11-2005 at 18:05

I tried the standard electrolysis today: 5V, ~20A, 20mL liquid NaOH (red devil brand), all in a nickel crucible. The annode and cathode were both very thick copper wire.

Electrolysis commenced with the standard period of violence and then progressed into a steady electrolysis with production of sodium and lots of tiny NaOH droplets flying around (and landing on my hotplate, probably reducing its lifetime considerably).Temperature control was hard, but I think I managed to keep it within acceptable limits for the most part.

I got that black solution early on, although this might have been a result of bismuth stuck to the crucible wall or temperature problems. It didn't seem to give me any major problems.

The sodium formed at an appreciable rate, but here was my problem: I couldn't get it out very well. The eyedropper I had quickly got clogged with NaOH and became unusable. My wire loop couldn't hold very much sodium because of its very low surface tension. Liquid NaOH kept solydifying on it, so I had to keep breaking of this crust. As a result, I couldn't remove the forming sodium fast enough. I eventually switched to sticking tweezers in the sodium and hoping to get as much sodium as I could where the NaOH solidified. I'll try to somehow recover my sodium tomorrow.

Is there something I'm missing here? I can't come up with a good way of removing the Na as fast as it forms.

I have and idea to fix this: confine the cathode (where the metal forms) in a glass tube with both ends open. The Na should form there and float at the surface where it could collect without fear of shorting the circuit out. The only problem is how long would the glass tube last? I know that liquid NaOH is notorious for destroying glass, but I don't know what kind of timeframe I'm looking at here (seconds, minutes, hours.) Also, would the eroding glass interfere with the electrolysis?

P.S.
One more thing. When I was cleaning up my equiptment, I noticed that most things stayed basic after repeated washings. Does anyone anticipate any problems with just leaving a small amount of NaOH there and letting the atmosphere do its work?

[Edited on 24-11-2005 by neutrino]

BromicAcid - 23-11-2005 at 19:40

A glass tube could be used. It will not just dissolve quickly into your melt, likely your melt will solidify around the glass and not really attack it, the problem being that if this happens the liquid within the tube will likely solidify as well, and if thats the case your sodium will rise up and just go to the sides of the test tube, so you'd probably need a tube a little bit wider then you would expect.

[Edited on 11/24/2005 by BromicAcid]

neutrino - 23-11-2005 at 20:16

Why would the NaOH solidify? Heating from the electric current should easily keep it molten, right?

BromicAcid - 23-11-2005 at 20:40

It was just my reasoning, that although glass is not really that conductive to heat, it might still be enough to wisk away some of the heat from the melt and thereby cool it where it touched the glass causing it to freeze. However this may not be the case as the resistance from the heating of the melt is right beneath the glass tube and the heat would rise and thereby melt the solid that would form there. So I guess you should just be wary that something might happen along those lines.

neutrino - 7-12-2005 at 17:44

I tried my idea a few days ago. In about a half hour of operation, the glass was eaten severely, some places had holes where I gently washed the tubes.

My electrodes were both thick copper wire, both were submerged about 3cm into the melt. My yield was zero, I guess this has to do with those current density issues mentioned higher up. How much 1mm diameter wire should be in my melt? The PSU was 20A @ 5V.

The NaOH turned blue after operation, indicating the annode was dissolving, although it doesn't look any thinner. The cathode was coated with a brown substance, probably some copper that had plated on, albeit not well.

Temperature control was a problem here because everything kept freezing in my 40mL melt. I guess it doesn't help that it was below zero when I did this. Next time I am doing it on a hot plate.

I did two successful runs with the loop method. I managed to collect about 1.5g of sodium of some unknown purity. It formed visible crystals when it solidified under its oil. Does anyone know what sort of purity I might have here? I will upload a picture if anyone wants to see it.

12AX7 - 7-12-2005 at 21:30

Probably 99.9% or better, metals are pretty pure when they form a squarely crystalline regulus.

I've only seen it for example in 99.99% (1099 alloy) aluminum, which makes crystal formations up to 1/4" wide.

Tim

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