Sciencemadness Discussion Board - A less-than mediocre attempt at Lead Dioxide!

A less-than mediocre attempt at Lead Dioxide!

Jstuyfzand - 1-10-2016 at 13:02

There is a myth, that a Lead Dioxide anode can be made using no Nitric acid...
As a High Schooler, without permits, in The Netherlands, this grabbed my attention rather quickly, since one of those anodes could mean I can electrolyze everything without decaying, making chlorates and perchlorates, and finally allowing an attempt at a Chlor-alkali cell.

This dream of mine lived longer than just now, I have scoured the Sciencemadness forums for information on the anodes, and I read through a disgustingly long thread on Anodes, 2 actually, and came out wiser, but no information about an acidfree procedure.

I stumbled across a video by Gooferking Science:
https://www.youtube.com/watch?v=bZMWEYiTtso

My hopes skyrocketed, but I remained sceptical, I starting using the awesome, accurate sciencemadness search engine and I got a few references, but all saying it was hard to make it work, and most likely, wouldnt.

I got my hands on a litre of battery acid and some lead wheel weights.
(Honestly, where does one get lead? And if you know a place for nitric...)

So I am now attempting to post some pictures, my hopes arent high...
http://imgur.com/a/zcZYO
^This gallery should contain all of the pictures

So me and my friend decided to spend our time melting down some lead with a crude campfire and then trying to get something out of it that resembles a cylinder, the result of our attempt was very mediocre but we figured it was ready for the acid bath.

On a different note, I just wrote a ****load of words and I pressed the refresh button, and got back here, just putting it out there....

Into the acid it went, we saw a current of 0.7A and at a 1.5V and the Cylinder was about 10 square centimeters so the Current density was 70mA per Cm2.
This was pretty high, and we will definitely improve upon next time we will attempt this.

The anode was discoloured with a brownish tarnish over it, this concerned us since we were hoping for a nice blackish grey color.
At this point we considered ourselves doomed, but decided to put it into the salt bath.
At 5V and 1A, shit hit the fan, the anode rappidly spewed brown crap into the solution and the Coating was quickly devoured by the harsh conditions in the cell.
Saddened by this, we decided to put our tears towards the sciencemadness community.

Summary:
Two 15 year olds desperate for a suitable anode for their totally legit purposed decide their evening is best spent dancing around a campfire with a pot full o lead.
Results were bad, and we are sad.

All joking aside, we are well aware that our procedure was less than optimal, we have very limited rescources and this was the best we could do.
We tried a method that works in theory but has proven very hard in practise, however, it was a nice learning experience, and we would love to hear your thought and opinions on out crude attempt, just, be nice eh!

I can already see the replys about the lead nitrate method, and I appreciate your reply, I really do, but there is barely any way I can get my hands on Nitric acid, let alone Lead Nitrate, to carry out that procedure.
We have a very barren situation here, no glassware, no fancy stirrers, and no permits to get anything Fun... I mean useful.

Anyway, thanks a lot for reading, it may have bin a bit shortened, but I the page refreshed after I tried to upload a file, so I am not trying that again, and I had to rewrite everything.

Also, apologies for wasting 10 minutes of your life, or 15, if you are dyslexic, and you cant get your head around my punctuation, because I know my friend wont have it easy...

Thanks!

EDIT: I looked at the photos one more time, and you may think the iron rod causes the brown discoloration.
We taped the rod to make sure this wouldnt happen, so that aint it

[Edited on 1-10-2016 by Jstuyfzand]

cryomancer - 1-10-2016 at 17:24

Jstuy

I know your pain man, its hard to find nitric acid and even harder to find cheap even in the US. I cant say that i have made it but you were one foot in the door with the battery acid, its Sulfuric acid(usualy at least 30%) see if you can find Spectracide brand Stump remover, if you can thats your golden ticket to Nitric acid. Spectracide is almost pure Potassium Nitrate, just simply do a little math to balance the equation and react the battery acid with the stump remover and you have crude Nitric. Its not great but it still does the job.

The best source of lead for me is getting lead shot for shotguns or if you can go to say Midway USA and look under their bullet casting section you might find lead there. Otherwise you might have to buy it online. Best suggestion from me: get crafty and look around i have been surprised by what some OTC stuff has in it.

But never give up on it though, i am in your position as well (high school, at least one parent that doesn't know chemistry and is always asking if you are making a bomb,(at least my mother took a lot of chem in collage) but so far you have done more than i have so just look around and keep searching)

Good Luck,
Cryo

Jstuyfzand - 2-10-2016 at 01:01

Cryomancer

I was pleasantly surprised with the accuracy that you described my situation with, especially the "are you making a bomb" part.

I got my hands on some KNO3 and I want to boil the acid further to concentrate it for the nitric acid making.
I dont have any distilling glassware though, I usually improvise but I don't think that would be smart handling strong acids pike nitric.
I hope to buy/get an old distillation apparatus somewhere.

cryomancer - 2-10-2016 at 10:45

if you cant get a distillation apparatus at all then you can just boil the crude Nitric Acid down to concentrate it to about 68% but you will have a huge amount of potassium sulfate impurities.

It would work but make sure the KSO4 wont interfere with the reaction.

United Nuclear sells a decent setup for 160$ USD(might just get lucky and get one for Christmas) also check Ebay, you will need somewhat controllable heating and if a lab hotplate is to expensive then see about getting one of those cheap electric one burner hot plates that will cost maybe 20$ and just use a metal bowl for an air bath so you can get a decent amount of control on heating

Jstuyfzand - 2-10-2016 at 11:11

Im in the process of building a 1000C kiln, I plan to just put a metal slab on it and use that for heating.
I have a voltage regulator on it so I have some degree of temperature control.
I might actually ask my high school chemistry section to perform the reaction, as a demonstration for students or something like that.
The wildest thing we ever dit was electrolyze salt water, they dont have a lot of money for these demonstrations.

[Edited on 2-10-2016 by Jstuyfzand]

zwt - 2-10-2016 at 11:18

I wonder if the electrolytic deposition procedure detailed in the first post of this thread could be done with acetates instead of nitrates. Reasonably pure copper and lead acetates could be prepared from the metals, white vinegar, and air, but without a distillation apparatus, it will be time and labor intensive (the slow dissolution of the metals, followed by evaporation of the dilute solutions, filtration, and multiple recrystallizations for usable purity). Lead acetate baths without copper or rotating anodes were considered briefly in the big PbO2 electrode thread, with mixed results. The main issue I'd expect is the acetate decomposing to various side products when subjected to electrolysis, contaminating the bath.

As the nitrate method has proven reproducibility, here's a nugget of wisdom on producing nitric acid with very meager equipment:

Quote: Originally posted by Polverone

I use nitric acid only rarely. I don't use it for nitrations (I have no convenient place to enjoy any nitrated materials at this time). Therefore I have invested very little effort in my setup. I put powdered potassium nitrate and sulfuric acid in a glass soda bottle and turn it on its side. The tapering glass mates nicely with a glass teriyaki sauce bottle's mouth. The first time I padded the joint with teflon tape but there's very little loss of product even without it. The sauce bottle is wrapped in plastic bags of crushed ice/water. The whole setup is balanced on a couple of cinder blocks so that the rear half or so of the soda bottle is suspended in the air. This I heat with a bunsen burner held with metal tongs (to save my hands should the crappy glass suddenly shatter). This setup is low- yield and low-effort, perfectly adequate for my current needs.

[Edited on 2-10-2016 by zwt]

phlogiston - 2-10-2016 at 12:39

These guys deposited lead dioxide from a sodium plumbite solution, which they prepared by dissolving lead acetate in 4M sodium hydroxide solution:
Insoluble anode of -lead dioxide coated on titanium for electrosynthesis of sodium perchlorate

lead is easy to get in the Netherlands. It is used for roof covering and most large hardware stores sell it (ask for 'bladlood' if you can't find it). I believe the alloy is usually >99% lead, with the main alloying metal being copper.

If you did not already, read the long lead dioxide thread and pay particular attention to the parts discussing the substrate.

Also, you are young, your brain is developing and very sensitive to lead poisoning. Please be extremely careful and hygienic when working with soluble lead compounds! This project is not worth permanently losing IQ points for.

[Edited on 2-10-2016 by phlogiston]

Jstuyfzand - 2-10-2016 at 13:56

Quote: Originally posted by phlogiston

These guys deposited lead dioxide from a sodium plumbite solution, which they prepared by dissolving lead acetate in 4M sodium hydroxide solution:
Insoluble anode of -lead dioxide coated on titanium for electrosynthesis of sodium perchlorate

lead is easy to get in the Netherlands. It is used for roof covering and most large hardware stores sell it (ask for 'bladlood' if you can't find it). I believe the alloy is usually >99% lead, with the main alloying metal being copper.

If you did not already, read the long lead dioxide thread and pay particular attention to the parts discussing the substrate.

Also, you are young, your brain is developing and very sensitive to lead poisoning. Please be extremely careful and hygienic when working with soluble lead compounds! This project is not worth permanently losing IQ points for.

[Edited on 2-10-2016 by phlogiston]

We already considered Bladlood, stuff is very expenisive though, Ill get by scrapping I think.

A bit more about the safety though, we melted it in a small fire outside, trying to stay away from the smoke and everything, just working with the pure metal.
And of course thoroughly washing hands afterwards.
How big is the danger when working with lead metal (Not compounds) in situations like this?

Zwt, that setup sounds very easy and I would love trying it.
But my parents know a bit too much about chemistry that Acid vapors in an improvised vessel is a big nono!

phlogiston - 3-10-2016 at 06:31

Just melting and casting metallic lead is not very dangerous, provided you do not strongly overheat it. Most sources say stay below 450-500 deg C. Stay out of the fumes, and wash hands/arms/face. Soluble compounds of lead are much more dangerous.
Note that electrolysis often generates a fine spray/mist that is easily inhaled.

If you are looking for free lead: if you have a metal detector, you can find small amounts of lead in fields nearly everywhere.

Jstuyfzand - 3-10-2016 at 14:14

Quote: Originally posted by phlogiston

Just melting
If you are looking for free lead: if you have a metal detector, you can find small amounts of lead in fields nearly everywhere.

What would be the source of those small amounts of lead though?
In America, I assume it would be lead from bullets, here in the netherlands though, not so many bullets.

phlogiston - 4-10-2016 at 01:39

Yes, Dutch field also contain many bullets. People have been shooting rabbits and ducks and fighting wars for hundreds of years and nobody ever removes the bullets. As a result, you'll find significant amounts of lead, much of it in the form of old musket balls.
A collegue with a metal detector has a large bucket of them.
You could also ask kindly at a shooting range.

A discarded car battery is another cheap/free source of lead, but disassembling it is messy. Take care not to contaminate your parents house with lead sulphate/dioxide powder. The main alloying metals in car battery lead alloy are antimony, calcium and selenium

Fulmen - 4-10-2016 at 05:32

Quote: Originally posted by phlogiston

Nice find, has anybody tried this approach?

Jstuyfzand - 4-10-2016 at 05:38

Quote: Originally posted by Fulmen

Quote: Originally posted by phlogiston

Nice find, has anybody tried this approach?

They plated it on platinum though, defeating the whole cheapness factor

Fulmen - 4-10-2016 at 06:46

Yeah, I saw that too. Not sure if it's absolutely necessary or not, could be a safe bet as their goal was to characterize the PbO and not the substrate.

yobbo II - 5-10-2016 at 12:41

The following US patents used alpha somewhere in the anode

US 5545306
5683567
5431798
5391280
4064035

phlogiston - 7-10-2016 at 15:00

Interesting, so USP5431798 suggests at least one possible alternative to platinum substrate, namely tin oxide.

One problem with substrates for lead dioxide is that they must satisfy two conditions:

1. The material must remain conductive if it is in contact with lead dioxide (eg. a conductive oxide or a metal that forms a conductive oxide such as silver).

2. It must not disintegrate too quickly if small defects in the lead dioxide layer permit the electrolyte to contact the substrate.

A practical problem I would expect to occur with plating alpha-lead dioxide from alkaline solutions is that spongy lead metal will form on the cathode, and cause a mess and eventually even shorts between the electrodes. In an acidic plating cell, this is easily solved by adding a little soluble copper salts. Copper plates out preferentially at the cathode then, and this forms a dense layer. But copper hydroxide would precipitate in the alkaline electrolyte.

zwt - 7-10-2016 at 15:25

Quote: Originally posted by phlogiston

A practical problem I would expect to occur with plating alpha-lead dioxide from alkaline solutions is that spongy lead metal will form on the cathode, and cause a mess and eventually even shorts between the electrodes.

They recommended a cathode with an "area about 20 times larges than that of the anode".
Wouldn't the low current density promote the formation of a thin, dense plating of lead, rather than "spongy" deposit you describe, or the "shitload of stringy dendritic crystals" described as forming in this copper-free (acidic) lead dioxide deposition cell?

Also, it's been noted that the use of platinized titanium as a substrate makes this procedure impractical for amateurs on a budget. What problems are most likely to occur when graphite is used as the anode/substrate in a plumbate bath? As an anode in such strongly alkaline conditions, is the graphite likely to oxidize too quickly for the lead dioxide to adhere well?

[Edited on 8-10-2016 by zwt]

Fulmen - 18-10-2016 at 12:24

It turns out that lead plumbite is fairly easy to make. Rather than starting with metallic Pb I started by turning my Lee Pot to full power. By stirring the surface lead oxide is formed pretty fast, this was then dissolved in 4M NaOH. Upon cooling it produces beautiful glistening crystals, the remaining liquid can be decanted to dissolve more lead oxide.

Chlorine - 27-11-2016 at 16:07

If you go to an auto repair shop and ask politely, they may give you some free scrap lead. If there are none around you, there's always range scrap.

Range scrap:

https://postimg.org/image/ivig8pbbd/

Scrap ingots

https://postimg.org/image/ycbitwej7/

CrossxD - 26-2-2017 at 03:23

I think the easiest way to make lead dioxide is:
start with soluble lead salt (nitrate, acetate) add sodium hydroxide 4 mol per 1 mol of lead salt.... white percipitate will appear..... heat....percipitate will dissolve, you have solution of sodium nitrate (acetate) and sodium plmbite (Na2PbO2) add hydrogen peroxide (or let it stand on air for long time and than add hydrochloric acid and brown percipitate would form
Pb(NO3)2 + 2NaOH-> 2 NaNO3 + H2O + PbO
PbO + 2NaOH-> Na2PbO2 + H2O
Na2PbO2 + [O]-> Na2PbO3
Na2PbO3 + 2HCl-> 2NaCl + H2O + PbO2

macckone - 26-2-2017 at 11:12

Lead Acetate is easier to make considering the
difficulty of buying nitric acid and the ease of
getting vinegar. Sources of easily obtainable
nitrates are now scarce in many european
countries.

Solutions to the nitric shortage include
home built ostwald reactors (copper can be used
as a catalyst rather than platinum) or birkeland-eyde
reactors. Of course if you can get any non-urea
based nitrogen fertilizer, you can make nitric acid.
It is just a pain in the butt.

I highly recommend birkeland-eyde reactors
as a starter project in mad science. They look
incredibly cool and produce a hardish to obtain
chemical but don't electrocute yourself.