There has been incessant arguing on the quentron thread about a device that has been running for 50 years, seemingly in contradiction to 2LOT. It deserves its own thread and I hope that this is where the argument will be continued.
Here is an article explaining to the reader the background of the Karpen pile, does it work by harvesting ambient thermal energy I do not know? I am an expert on quentron and I will release info when we are ready to sell devices, not until then. So here is the article
KARPEN PILE ARTICLE
Now investigators of an amazing object stuck in the dusty corners of an obscure Romanian museum may have found the next best thing:
Whether a battery that has operated continuously since 1950 without a recharge can be termed perpetual may be open to debate, yet the fact remains that the remarkable device has never ceased working and doesn't look like it's about to give up the ghost anytime soon.
The battery that's been pumping out electricity faithfully for 60 years was built by Vasile Karpen.
Karpen's Pile
The director of the Dimitrie Leonida National Technical Museum in Romania, Nicolae Diaconescu, when interviewed about the battery by the Romanian newspaper, ZIUA (The Day) said, "I admit it's also hard for me to advance the idea of an overunity generator without sounding ridiculous, even if the object exists."
That the battery—called "Karpen's Pile"—exists is indisputable.
When Karpen built the battery he claimed it would function forever. Although decades ago engineers and physicists that studied it believed it would stop working soon it never has stopped.
Those engineers and physicists are now long dead, but the amazing "perpetual" battery keeps humming along.
Patented in 1922, most scientists that have studied it over the ensuing decades cannot fathom exactly how or why it works.
The Karpen's pile that sits in the director's office at the museum was a prototype built to Karpen's specifications. It has two series-connected electric piles that move a small galvanometric motor. That motor spins a blade that's connected to a switch. Every half rotation the blade opens and then closes the circuit during the second half of the rotation.
According to some engineers that have analyzed the ingenious device, the blade's rotation is exactly timed to allow the piles to recharge themselves and re-establish their polarity before the next rotation of the blade.
ZIUA also reported that a measurement of the current established a steady one volt output—exactly the same as when the battery was first activated in 1950.
During the interview with the newspaper, Diaconescu added that "unlike the lessons they teach you in the 7th grade physics class, the 'Karpen's Pile' has one of its electrodes made of gold, the other of platinum, and the electrolyte (the liquid that the two electrodes are immersed in), is high-purity sulfuric acid."
The museum director also asserted the battery could be made larger to produce more power.
"The French showed themselves very interested by this patrimonial object in the 70s," Diaconescu said, "and wanted to take it. Our museum has been able to keep it, though. As time passed, the fact that the battery doesn't stop producing energy is more and more clear, giving birth to the legend of a perpetual motion machine."
Recently, some leading European electrical engineers proposed that the device creates power by converting heat into mechanical energy. Diaconescu doesn't agree.
The fascination over Karpen's Pile is fed by the possible physics behind it. Some who have studied the theory Karpen created explaining the functionality of his battery believe the engineer's device violates the Second Law of Thermodynamics.
Others scoff at that, but then go on to argue that it may well be an application of the physics inherent in drawing power from the theoretical "Zero Point," thus making it a Zero Point Energy device.
Whatever the cause, understanding the driving principle underlying Karpen's Pile might revolutionize both physics and the search for alternative energy sources.
that WASN'T ALL THEY KNEW @sarkeizen.they KNEW the same galvanic rules that you find in the college textbook today.why debate about it for 70 years and still on?we don't know what's in the oxford bell cell.we KNOW what's in the karpen cell,since THEN.we even REPLICATED it over the years,PLAYED with it,shoved it into labs(russian,chinese,french,german)yet no consensus.why.
@profitis,
For the readers info can you fill in some details.
I see the Karpen pile produces 1 Volt, but can you tell us something of its power output per cm2 of electrodes? clearly if it can run the motor that cycles the device it can produce useful output, and the director of the museum states it can be scaled, so can you tell us if it has been applied to power something external to the pile?
Do you feel its output can be dramatically increased, perhaps in a manner similar to ultra caps where we can have incredible surface area in a compact form.
Apart from Gold and Platinum, what other combination of metals work and how do they differ in output?
thanks
Sure phil.you're looking at roughly 0.2v/single couple so he had to stack a whole bunch together into 2 piles,the power supply alternating between them with each rev of the motor brushes.that motor would definitely require several milliampere to do its thing so it was a fair amount of power coming out there.one square cm of a single couple(platinized platinum) will give roughly 150microamp at the top of the powerburst curve.if it were a normal cell the electrodes wouldve corroded away 40 years ago at that power draw. Naturaly its power can be fairly increased nowadays with modern fuelcell platinum sponge tech but the original is just way too costly for. commercial use.apart from the 02/air based cells you want to try the hydrogen based cells eg nickel/silver or palladium/silver variety.they differ enormously in power output versus the original.between ten to hundred times power density.scary stuff @phill
@profitis, so you are saying with the right combo of metals, a stack of layers and using sponge forms, it would be possible to have a pile that outputs say 2V @ 1A in a volume of, say, 1 Litre, is this correct?
Judging from what I've seen on smaller samples I cannot say no phill.
@profitis, what is the mechanism (please state it in some detail if you can) that you believe is responsible for the production of the emf?
Quote from: Philip Hardcastle on May 23, 2014, 08:08:44 AM
@profitis, what is the mechanism (please state it in some detail if you can) that you believe is responsible for the production of the emf?
Rex Research adds more. It is said to convert ambient heat into electricity, but how gold and platinum electrodes in high purity sulphuric acid does this is anyone's guess:
http://www.rexresearch.com/karpen/karpen.htm
.
Gas overpotential differences phillip.the rate of forward and backward reaction of gas electrochemical equilibrium eg O2 + 4H+ +4e- >< 2H2O depends on 1) the catalyst material on which it takes place and 2)the availabilty of reactants(concentrations). The catalyst material eg smooth gold is going to promote the backward reaction rate faster than sponge platinum which promotes the forward rate faster.this is due to many factors eg work function,catalyst step mechanism,adsorbtion etc.since the rate affects potential there's a different gas potential on gold than platinum.this well known as gaseous galvanic OVERPOTENTIAL or more recently UNDERPOTENTIAL depending on wether the potential is over or under the standard gas potential.so the original karpen cell is simply an oxygen overpotential differential cell.O2 passes galvanicly from one electrode to the other until potentials equalize when switch is thrown.when switch is cut the gas that was transferred simply diffuses back again.no net change after a complete cycle thus it is able to repeat with no energy expense on our part.a kelvin breach in all its glory.
@profitis
Your explanation is fine so far as it goes, but I feel that it is only an overview of the real issues.
Given that the device has been running for 50 years with no sign of corrosion, and has done a lot of useful work, I have no reason to believe it (Karpen Pile) is anything other than solid proof of some mechanism, and perhaps a Demon, but clearly it has been studied by many scientists and no concensus seems to have been reached. This makes me think that you would need to drill down an extra level to have a proof of a Demon driven by ambient thermal energy.
On the same idea as a Demon, if I play the Devil's advocate I could say it is not thermal but driven by light, do you know if tests have been made to rule out such things?
As you know the issue at stake is that of proving, either by rigorous maths, or by physical experiment, that there is asymmetry. This is the issue that almost all ideas fail on, ie the thermal ratchet of one kind or another.
So you see this (Karpen) as asymmetrical, but you have not sufficiently explained how to me, as yet, even though the idea of electro-chemical equilibrium is a good start, your 02 + 4H + 4e >< 2H2O does not have an energy term (ie ambient thermal energy input). So can you expand your explanation?
Regards Phil
Quote from: Paul-R on May 23, 2014, 09:34:43 AM
Rex Research adds more. It is said to convert ambient heat into electricity, but how gold and platinum electrodes in high purity sulphuric acid does this is anyone's guess:
http://www.rexresearch.com/karpen/karpen.htm (http://www.rexresearch.com/karpen/karpen.htm)
.
Thanks Paul.
@profitis, the more detailed article raises a question or two that perhaps you can answer.
Is it the case that a Karpen cell of figure 1 (2 liquids) provides a continuous output?
If so is there a plot of its electrical output v ambient temperature? if not why not?
Figure 1 with 2 immiscible liquids and 2 same eg platinum electrodes:amyl alcohol dissolves a different quantity of O2 gas and electrolyte than the bottom layer of water and thus sets up both a gas and ionic concentration potential difference between electrodes ie. Its a concentration cell and the nernst equasion applies there.since the concentration differences can never even out permanently it too violates kelvin rule.fig2 is the variety that I used for example in quentron thread where 2 same electrodes have different equilibrium exposure to gas resulting in a strictly permanent concentration difference.the nernst equasion applies here too.fig 3 is of the original karpen pile variety,the one we're interested in.fig 3 is explained in terms of gas overpotential differences or more easily in terms of a phenomena known as catalytic gaseous SPILLOVER.so figure 1 and 2 are simple concentration cells that have a concentration difference AT rest equilibrium.that'swhat makes them different from all other concentration cells which are not at rest equilibrium when there is a voltage present.like any cells their performance and efficiency goes up on a warm day but they work just fine in siberia too so they,l throw heat to the environment on discharge and then the environment will throw the exact same heat back into them when they rest for recharge,contrary to kelvin rule.why? Simply because they possess a voltage AT maximum rest equilibrium.fig 3 is better pictured in terms of gaseous SPILLOVER which occurs due to factors like gas concentration differences,adsorption differences,work function differences etc.the electrochemical overpotential difference explained for this type cell is simply the electrochemical manifestation of the gaseous spillover gradient force.we need to go deeper into gaseous spillover to get get to the bottom of this phil because the assymetry will become more apparent there as will the thermodynamics.
ok phil,was getting lonely here.the heart of the matter is a CONTACT POTENTIAL DIFFERENCE. This is what ties the karpen device to your device.a piece of zinc and a piece of copper shoved in electrolyte eg in the daniel galvanic cell will give a voltage exactly equivalent to the contact potential between the two metals in vaccuum.the galvanic setup is just one way to utilize this and it is spontaneously irreversable.the contact potential difference between gold and platinum under oxygen is utilizable galvanicly and totaly REVERSABLE.thus it is essentially the work function differences at play here in a totaly reversable setup.the oxygen gas and electrolyte in the karpen setup are merely a spectator piggyback molecules for carriage of electric charge through the circuit..and make it useful.
No the unanswered question of great importance is this one:
"On the same idea as a Demon, if I play the Devil's advocate I could say it is not thermal but driven by light, do you know if tests have been made to rule out such things?"
Got it phil.First of all,and I must say this here and now to all demonologists,ou seekers etc: get the idea of maxwell demon out of your mind.its an erronius idea that a system must possess one in order to circumvent kelvin rule eg..the system as a whole must simply have at least 2 superimposed assymetrical maximum entropy states.if its got those two states in one then its a contender to bypass kelvin rule.its the orderliness of the system as a whole that counts here. When you begin 2 experiment with karpen-type cells you will quickly notice that it has nothing to do with light,sound,vibration phil as its power-outage does absolutely not correlate with variencies of these natural resources.ie you can shove a cell in a lighted room or in complete darkness and the power changes zilch.the power densities that I have seen,even of the weaker versions have also zero correlation with noise.you can take a cell to the furthest jungle and it works exact same as if your in the middle of a city peppered with radiowaves.the power-discharge-pattern of these cells correlate only with what you'd expect from the nernst equasion or from textbook electrochemistry.it is too obvious when its in front of you.
I also want to add: the rules of electrochemistry are set in stone so to say that the energy is coming from 'somewhere else' and not from common gaseous overpotential differences is like expecting a normal batterie's power to be coming from mars when its just common elecrtochemistry.
@profitis, you say that nothing external varies the output of the Karpen, what I would like to know is are there any experiments supporting that, and if so can you give me a link?
As to the issue of the need for a Demon, I think your statement is too wide, I agree that there are some 2lot violating ideas that do not fit with the classic demon, I say sebithenco is one as it does not require energy to be expended to do the sorting of kinetic energies, but I am not sure about if the Karpen does costless energy sorting, or not.
Have you actually built a Karpen? and if so have you tested it photo sensitivity.
As you may know light can cause impermanent chemical changes, the fact that a Karpen cell exists in a jar in a non light shielded room, and has worked for decades doing useful work, would lead any reasonable person to ask if the diurnal effects are an issue that need to be explored. You cannot declare the Karpen to be a perpetual cell if you have no proof that it is not simply a photocell.
I am not saying you are wrong, but I am simply stating that people questioned the sebithenco on the same issues, I had to prove no photo or Rf influence, no temperature gradient, and no radioactiviy before I could myself conclude that it was a proved violator, then I had other people do the experiment (5 different people in 5 different locations) and confirm my findings. Then I carried out 100s of experiments to test everything I could that would influence the Sebithenco, and all this has been over years, only with all that can I state with a scientific level of proof that the Sebithenco is a 2LOT violator. I cannot simply accept from you a blanket statement that nothing can influence the Karpen output, and in fact if there is no correlation with ambient temperature it suggests that the Karpen's energy is not coming from heat. So if you have some evidence re putting the karpen in a controlled environment you should state it now, otherwise I cannot see much point in discussing the device further.
Mr hardcastle..either the suggested cells I have diagrammed will power an ipod or radio for its FULL lifespan anywhere anytime OR it will not.nothing inbetween.it is not of commercial interest wether it is a 2lot violation or not.that is purely a scientific curiosity.but for the sake of scientific curiosity if we are to agree with the laws of electrochemistry then we must go by them and nothing else.if there is an gradient available for electrochemical catalytic gaseous spillover then by the suggestion of textbooks,it must happen.so let us simplify this even further to make it more clear,let's cut out the electrochemistry alltogether: we take a catalyst particle eg platinum and a substrate particle eg carbon,shove them under hydrogen and contact them 2gether,the textbooks tell us that spillover will take place,who are we to argue? We now seperate them again..what happens now phil?
Yoi talk about separating real world things as though the energy to do that is zero.
All I know of the Karpen is that there is one, not yours, that has been outputting a small amount of useful power for IRC 60 years. What I do not know is if it gets energy from the environment or chemically, but since the device has not corroded to total mush then I must conclude it is getting energy from an external source. So the question is; is it thermal, light, RF, vibration or something else?
So far you have not given me any information that can answer this most basic question.
As to LAWS, if i do not respect the 2nd Law then there is little point in asking me blindly to accept another law.
My work has always been to get to the essence of what is going on when we see some effect, whether that is thermionic or otherwise, so if I can get a handle on the Karpen I would need to understand the action at an atomic or molecular level, in other words given 2 chemical equations that you would say are reversible I would need to know the mechanism that drives them one way and then the other, somewhere in that understanding we would need to see a flow of energy if it is at times endothermic. Again for all I know the secret to the Karpen that has been having scientists scratch their heads for the last 60 years could be light or even biological.
Profits I am not being difficult but I know how the sebithenco works and how it is a 2LOT violator, but as yet I have no real understanding of if the Karpen violates 2LOT, and I suspect it is a rational conclusion to say there is a mystery to be solved, otherwise it would seem strange that 100s of scientists have failed to explain it if all it is, is a simple chemical equation pair.
The only single question you need to ask yourself mr hardcastle is this: is catalytic gaseous spillover from one particle onto another,100percent reversable.it boils down to this and this alone. If it is then its a clean violation of kelvin rule.if it isn't then its not.so its either A or B.nothing inbetween
The question is, has it been proved?
If we do not know the effect of it being in a lead box, then we are only guessing as to whether it is 100% reversible.
You have studied this, you tell me the evidence that supports your view that it violates Kelvin.
Do some research mr hardcastle.See if you can theoretically disprove it.search every angle because if you can't theoreticly disprove it then ones confidence in it goes high.all the cells which I've built work just fine.I guess the only way to really prove anything regarding a 2lot discrepency to oneself is to physically build, test,retest,retest etc. Do you have a lab at your disposal phil?
Profitis, I have no interest in repeating what you have done, my business is thermionic power and its roll out, your interest is Karpen, but what you intend to do with what you believe works is not clear.
I am making tiny cells to power Cochlears using body temperature, and other technology (20th August) to enable large scale power production at higher temperatures. For what it is worth I can tell you that if you can build a tiny sealed Karpen cell for a few dollars that works forever, but only at a few mW, it is still a worthwhile product, can you do that?
The devices I am providing to Cochlears and others will cost about $100 per mW, so you could beat me if yours is small, sealed and eternal with a ticket price of $50.
No I'm just looking for a nice comfortable job mr hardcastle.preferably overseas america,uk.I don't have the cash for development, rollouts.I'l be in my element in a well equiped lab and go ballistic with my ideas.I think your going at the right practical angle now with high temperature thermionics as opposed to the uncertain power density of the yet-to-be-made quenco.I've seen karpen cells of similar power as your battery but I'm only just touching the surface of the whole pandora box here.there's too many possibilities.
Hi Profitis, sorry I cannot offer you a job, but please feel free to keep in touch with me off this site.
The issues with built quentrons were not that of total failure, they in fact achieved a part success, but we have had to go back to the drawing board to understand why the quenco in tunneling mode did not perform as Sebithenco did in ballistic vacuum, the answer was very subtle and way beyond this thread, but briefly it was about asymmetry that was not effective when using a graphene barrier, we have fixed that now. I will put together a paper on the subject for arxiv after we have completed all the PCT patents, quantum physics is a very strange beast and it (the quenco story) should make interesting reading.
Regards
Phil
Thanks phil I'l keep in touch (-:
Quote from: Philip Hardcastle on June 04, 2014, 10:23:01 PM
Profitis, I have no interest in repeating what you have done, my business is thermionic power and its roll out, your interest is Karpen, but what you intend to do with what you believe works is not clear.
I am making tiny cells to power Cochlears using body temperature, and other technology (20th August) to enable large scale power production at higher temperatures. For what it is worth I can tell you that if you can build a tiny sealed Karpen cell for a few dollars that works forever, but only at a few mW, it is still a worthwhile product, can you do that?
The devices I am providing to Cochlears and others will cost about $100 per mW, so you could beat me if yours is small, sealed and eternal with a ticket price of $50.
hi Philip Hardcastle,
It seems i have already released free energy device some time back which can be run "24/7" merely on body heat as long we are alive(6c difference,36.5c body -> 30c room temp ) at one tenth the cost < $10 as compared to your estimated $100 per mW.25mV starting voltage for my case.
http://www.youtube.com/watch?v=Fzww6yPQMrg (http://www.youtube.com/watch?v=Fzww6yPQMrg)
That is just my version 1.0 which needs 4 fets in parallel.The version 2.0 which i did not bother releasing merely needs 2 key components 2SK170 and ZTX1049(or any ultra "low vce" drop transistor) in parallel configuration.Many people have duplicate my v1.0 device with successful results.It's free for all to replicate.
I have quickly lost interest in that free energy device which merely produce power in mW.
Moving on to KW power with some other experiments which i am doing R&D work at the moment which runs into few thousand dollars partially due to shipping cost as well.
(Details will only be released provided if i am successful) :D
"Doing business related to electronics is kinda tricky these days if it's easy to reverse engineer and further improved from there by some other companies"
50ml is the same size as some of the larger ipods @madebymonkeys.some large ones use same size bat as the small ones.I don't know if I'l get it right for this task unless I find a way to get the dc current flow continuous as opposed to burst curves.if I can get the current flow continuous then the whole ballgame changes dramaticly. That's why these are best suited for pulse circuitry.what about watches @madebymonkeys.why do people buy solar and kinetic like hot cakes?
Yes cellfones have just about made ipods obsolete @sarkeizen which is why I want to focus on remotes,watches,clocks.these are all very much here to stay so it boils down to the factors that would make everlasting these attractive to buyers,manufacturers.pocket radios are still big.shortcircuiting is the best way to prove no galvanic corrosion via unchanging wattage when in use.no chemicals are 'burned' up.
Thanks profitis.
As to your Karpen, if you believe 30cc can yield mW, why could it not provide Watts?
A flat plate capacitor deliver pF, one with the right intervening materials delivers uF, and then ultraCaps deliver Farads, surely your Karpen could benefit from some similar effect of increasing the surface area by a factor of 1,000x or even 1,000,000x, in which case just 1cc could be Watts, is this possible, and if so what would you need to make an ultra Karpen cell? or should you keep that quiet and patent something first?
So what's going to happen on August 20th?
Quote from: orbut 3000 on June 24, 2014, 10:13:58 PM
So what's going to happen on August 20th?
Wrong thread, this is for Karpen Piles.
Yes phil the more surface area crammed into small space would widen the discharge curve closer to a battery but it would still be subject to how much current drain is on it.an redoxultracap is the closest thing to it yes.ipods need steady continous large currents for long periods so I have no idea how long such a thing would perform before needing rest for recharge. Patents are out my financial league so somebody is going to have to do that for me or for themselves and me,if its worthwhile.
@profitis, take out a provisional to cover the work you are doing, that will cost you a modest amount and give you a year to work on the idea, discuss it with scientists, and to offer it to financiers.
I remain open to the idea that the Karpen is a real 2LOT violating technology since the device has not been rejected by science but seemingly put into the mystery category. I assume that there is some evidence of output to temperature correlation, and I also assume that it has been tested in a blackout condition and with an iso-thermal chamber.
If there was enough evidence and some plan as to how to make a W/cm3 then I might be able to get you some support out of a few universities, but you would need to provide solid proof that the basics had been covered.
My email is pjhardcastle@gmail.com
I'm aware of provisionals thanks phil. Yes they're definitely not stupid,they mustve tested the ins and outs of it ages ago and obviously something is fishy because of no official consensus.I've gotten a few very interesting documents off the net from publications by scientists who had studied it that are years old indeed indicating a 2lot violation. thanks for your offer to help,I might take it up as soon as I get a more full picture of the capabilities. It is truly a pandora box that may yet yield some diamonds or as sarkeizen calls it 'magic'.
I don't see seiko and co complaining about loss of buisness @sarkeizen so you may have overlooked something.the kinetic and the solar are hot sellers,probably more because of tech-nuts trenders buying them up as opposed to worrying about battery life.watches and clocks with regular batteries are boring,there's other reasons to buy an everlast.as I've said many times before,a combination of textbooks and lack of reason for irreversability is why humans should put their faith in my statements here.
Quote from: Philip Hardcastle on June 24, 2014, 10:49:37 PM
@profitis, take out a provisional to cover the work you are doing, that will cost you a modest amount and give you a year to work on the idea, discuss it with scientists, and to offer it to financiers.
I remain open to the idea that the Karpen is a real 2LOT violating technology since the device has not been rejected by science but seemingly put into the mystery category. I assume that there is some evidence of output to temperature correlation, and I also assume that it has been tested in a blackout condition and with an iso-thermal chamber.
If there was enough evidence and some plan as to how to make a W/cm3 then I might be able to get you some support out of a few universities, but you would need to provide solid proof that the basics had been covered.
My email is pjhardcastle@gmail.com
I haven't found much scientific testing on Karpens Piles at all on the web, just a guy measuring 1V with a DMM set to the 1000V range or something!
Is there a proper teardown and analysis somewhere?
There's one pdf on the wikipedia article for nicolae vasilescu karpen @madebymonkeys. www.en.wikipedia.org/wiki/nicolae_vasilescu-karpen . Go staight down to the bottom romanian reference from dogaru and cazacu from the society of inexhaustable energy. I'm going to see if I can make something impressive enough for your prize offer sir before the rest of the year is out.
and you forgot the watch stats of china? There's money in gizmo watches, period mr sarkeizen. Absence of evidence for a 2lot-obedience from something straight out the textbooks sticks out like a sore thumb don't be silly @sarkeizen.name one instance of a textbook principal that we cannot show enjoys 2lot besides this one..cmon try.. Its this which rules out an argument from 'ignorance'.
Quote from: profitis on June 25, 2014, 09:33:20 AM
There's one pdf on the wikipedia article for nicolae vasilescu karpen @madebymonkeys. www.en.wikipedia.org/wiki/nicolae_vasilescu-karpen . Go staight down to the bottom romanian reference from dogaru and cazacu from the society of inexhaustable energy. I'm going to see if I can make something impressive enough for your prize offer sir before the rest of the year is out.
Hmm, I can't work out if that document is bull€hit or not tbh.
1. I can't make sense of the math.
2. The English looks like a poor quality google translation.
3. It's based upon assumptions rather than a teardown and analysis of his Piles.
Could it be that his Piles are just low self-discharge batteries connected to a low power load?
If his piles are so interesting you'd think that someone would have analysed them by now, right?
I understand that a teardown would be destructive but it would give scientists (proper ones) the ability to replicate them - that would (if it isn't a hoax) be valuable. If they can't replicate then its a hoax. If they can, then we will all be walking around with iPods and massive batteries.
Given that this guys piles are sat on a 'secure shelf' providing no scientific or novelty value to anyone, maybe an offer should be made to buy them. Hey, if the museum can't afford an acrylic box and a padlock then it may cost less than you think! Offer the guy a case of wine or some crack, you never know! :-* :o :( :D
@Madebymonkeys,you can show us that hydrogen or oxygen spillover is irreversable? Even on paper?
Quote from: profitis on June 25, 2014, 06:36:03 PM
@Madebymonkeys,you can show us that hydrogen or oxygen spillover is irreversable? Even on paper?
No, I can't show that because I don't know how or even understand what you mean...Even on paper!
Maths isn't my strong point at all. When I said I didn't understand the math I meant it - I didn't mean that it was incorrect :-[
What I do understand is that the document must be based upon assumptions unless the author has investigated Karpens dirty, stinking piles.
Has anyone successfully replicated the piles or even had the chance to analyse them properly?....please don't say the guy with the DMM from the old photo, the one who used the 1000V range to measure 1V (he could have touched the probes on his own piles and got the same result on that range!)! :o
Quote from: orbut 3000 on June 24, 2014, 10:13:58 PM
So what's going to happen on August 20th?
Rod Stewart and Carlos Santana at Jones Beach: http://jonesbeach.com/index.php?option=com_content&view=article&id=413:rod-stewart--santana-aug-20-2014&catid=56:concerts-2014&Itemid=100054
Spillover is the textbook principal that makes it work @madebymonkeys sorry I didn't explain.many labs round the world have studied it but I don't know to what extent.perhaps they couldn't find efficient cost/benefit ratio or it could also be that they weren't allowed to advance to commercial injection its hard to say.if they had noticed a law of physics discrepency then it wouldve been hushhush as indeed it was and is but with internet here nowadays documents from labs are floating up left,right and centre from ages ago.some speak only in formula language that only scientists understand,others speak english and mention a kelvin law discrepency straightout,no shyness.
@profitis, you are the expert on Karpen so I will ask you this;
Is it (in your opinion) possible for a working Karpen cell to have identical electrodes at opposing internal faces of a 1cm glass hollow cube, and to have a semi-permeable thin film midway between them such that one electrode is fully immersed in solution A, and the other in solution B?
Such an arrangement would allow the operation to work irrespective of its alignment with gravity.
If so then what would stop a Karpen cell being constructed just like a capacitor, and if so then why could it not be stacked thin film and 10 high with a surface area (per layer) equal to a laptop?
This is not my opinion, just a question as to what you believe could work.
Some guys from around here and other forums have replicated similar cells eg ibpointless from overunityreseaerch has a youtube up but they usually have not got basic electrochemistry skills enough to know mistakes or errors that I've seen there.I haven't seen a genuinly cool and open breakdown of the museum piece anywhere but I can understand why the museum keeper is very protective over the thing after all the to-and-fro round europe trips its been on.I've myself replicated a small original using gold and platinum and it definitely works as advertised.no galvanic corrosion whatsoever correlating to the current draw.
I'm going to answer u now phill..
Aha..The amazing thing about a karpen is that it can be fully submerged and shaken,kicked or thrown and it still works like a bomb @phil.diffusion of gases takes place even through the electrolyte so gravity isn't an issue.anyways you can have it in drycell form with gel electrolyte so long as there's some air in there.
Membranes will work ofcourse phil and yes you can roll it up in the same way as todays nicads are rolled up in the shell.
@profitis, if membrane are used, and thin film is employed, it seems that the the base of a laptop of area 1,000 cm2 (40x25) could be full covered by a Karpen pile, the requisite voltage being obtained by having 10 layers of 100um each, it would have a volume of 100CC and weigh a few hundred grams.
The question is what current would 1,000cm2 electrode area produce at say 320K (being the working temp of the computer), assuming that you have some knowledge of correlation with ambient temperature?
I'm going to email you now about this one @phil.
Hi guys, I've been trying to replicate the Karpen pile for fun, using platinized platatinum electrodes and other inert electrodes. Normally I plate a metal on one electrode and leave the other as platinized platinum. I've not been able to plate gold as yet but I've tried copper as well as a separate graphite electrode, both of which should not be touched by 1M sulfuric acid. I've achieved over 1V unloaded with the Cu/Pt combo and about 50 microamps short circuit current for a few days with stirring and nitrogen purging, after which I turned it off. The Cu/Pt is of course simple galvanic corrosion of the copper.
Graphite/Pt gave a smaller voltage and, without stirring, the short circuit current died quickly. I noticed bubbles around the graphite.
All I can deduce is that it is galvanic corrosion. Different potentials exist at each electrode, so when they touch and a current does flow, oxidation and reduction must occur at the electrodes to pass the current, except that Pt and Graphite (or gold) can't corrode, so H+ is slowly reduced at the more negative terminal and water oxidized at the positive electrode.
I still need to measure the individual potentials against AgCl/Ag of the electrodes, but find it hard to believe that there is enough difference to decompose water electrolytically, so there is still a small mystery, for now.
What electrolyte did you use for the Pt/Cu and how big is your Pt size @pomodoro.
I'm using a cell with fixed electrodes about 2 inches apart. The electrodes are about 1 x 1 cm, or 2cm sq total immersed area each. Electrolyte was 1M K2SO4. I realize this setup is only appropriate for low currents but its all I have platinum wise. The reason why I think Cu/Pt was not a good choice is because of the galvanic corrosion chart below.
Copper is too reactive with certain electrolytes even if below hydogen liberation potential @pomodoro but you're on the right track.try see what current you get with Pt and Ag in NaOH solut. under pure nitrogen (jewellers 925 Ag is fine etched prior in some nitric acid to make a bit of surface area) then compare under pure H2. Your graphite/Pt under vaccuum or nitrogen is capable of a tiny bit of water electrolysis at a time in bursts because the potentials of H2 and O2 buildup to a point correlating with electrode surface coverage concentration.
@pomodoro, well done for taking a practical approach.
I think the Karpen cell enigma is the best thing on this site (not counting my own work lol) and it is more likely than not something that keen replicators can work on.
The facts that I see is that there is a voltage and small current produced by a gold / platinum device that has yet to be explained, or contradicted. 60 years of operation of a device should raise more interest than it has. Sensible debate and attempts to falsify should be the way forward, not the negativity that comes from the usual suspects.
I am of the view that if a sealed eternal supply of less than 1cc volume could be made that gives out 1.5V at 2mA, then it has immense application in the form of implanted power supplies for things like the bionic ear (cochlear), pacemakers and neural stimulators.
If you guys can produce such a thing that you can prove is a 2LOT violation, then I can provide all the funding you would need to commercialise it, even though I am currently working (as profitis knows) to commercialise a competing technology.
Phil
Thanks, both of you. I'm happy put all my standard findings on here for anyone to view and utilize. I've got access to electrochem equipment which I only use for CV and ASV but can do lots more. However I am not an expert in electrochem, and needed to brush up. So when I came across Karpen's invention I got some motivation to find out how it works. Now I don't want to screw up anyone's potential to make money, so if anything unusual does come up, I might mention it but not very specifically, but any expected findings I will mention specifically.
Regarding the Pt/Ag experiment @profitis, I shall get to it as soon as I get back to work next week and report the results.
Quote from: pomodoro on June 30, 2014, 07:23:27 AM
Thanks, both of you. I'm happy put all my standard findings on here for anyone to view and utilize. I've got access to electrochem equipment which I only use for CV and ASV but can do lots more. However I am not an expert in electrochem, and needed to brush up. So when I came across Karpen's invention I got some motivation to find out how it works. Now I don't want to screw up anyone's potential to make money, so if anything unusual does come up, I might mention it but not very specifically, but any expected findings I will mention specifically.
Regarding the Pt/Ag experiment @profitis, I shall get to it as soon as I get back to work next week and report the results.
This is a great experiment and I was wondering about the results of this myself.
I wouldn't waste my time on electroplating anything but plated Pt electrodes versus a plated Au electrodes. The whole purpose is to
have the Sulfuric acid electrolyte not be able to touch the surface metal so that the cell can operate indefinitely. The 18/9 Stainless
Steel might be an interesting entity though. I doubt you can electroplate Stainless steel onto anything, but stainless steel might make
an interesting bulk core material. If the are pinholes in the Pt or Au electroplate surface perhaps a Stainless Steel core would inhibit
corrosion for a while eventually stopping corrosion at those pinholes. Obviously SS is more resistive then Cu but it may be more stable.
Please be aware of the negative consequences of any of the nasty Hexavalent Chromium ions from SS.
The other question is of how thick the surface coating layer is required so that the core materials electronegativity doesn't
"play-through" and affect the electrochemistry of the surface layer. I'm thinking of the ion porosity of those thin-glass
PH probes.
Once a minimum plated on thickness is determined one could do a cell cost calculation of the precious metals per square
electrode area.
I would not be surprised at the presents of some electrolysis of water in an operating cell. Though initially these might be due
more to the presents of impurities. There are catalytic systems for recombining hydrogen and oxygen gas if required. In fact
there are those catalysts are available in some acid/lead battery caps.
I think as has been mentioned that oxygen gas is playing a role in the electrochemistry of this system.
Good luck on your experiments
:S:MarkSCoffman
Quote from: mscoffman on June 30, 2014, 12:04:58 PM
I doubt you can electroplate Stainless steel onto anything
No, because it is an alloy. I reckon the iron would come off on its own.
But you could probably use vacuum plating or vacuum deposition.
True @phil its high time that people started to attack and disect ol karpens battery and its principal adequetly and bring it out of its mystery category.a few already have but they haven't been paid attention enough.
Looking forward to hearing results @pomodoro I've said a little more on this subject than I shouldve myself but had no choice in order to be taken seriously.
I owe you gratitude for starting this thread and supporting it @phil and I don't think competition would be a problem as I think every 2lot buster from you,me or others will have its specific duty commercialy,even some seemingly shitty ones with low power.anyway I might run to you for assistance in any case if something good comes along and take you up on your offer to help.
This is my rough plan at examining the pile.
1. Plate thick 24k gold onto a platinum electrode. Use non Platinized platinum for the other electrode, dip Pt in aqua regia to roughen surface.
Result - one cell of the Karpen Pile ready for testing when dilute Sulfuric Acid is used as electrolyte.
Expected observation- Very low voltage if any due to similar nobility of metals (reason why Karpenneeded two huge piles to get 1 volt).
2.It is believed cell turns thermal energy into electricity
By shorting electrodes with wire, a current should be able to be measured. Unfortunately this will be very low and any loss in temperature will be miniscule and immesurable with my equipment.
3.Electrode reactions.
Normally, when 2 dissimilar metals are connected and dipped in an electrolyte, one becomes the anode and the other cathode. For example take Zinc and Copper in a salt solution. The less noble of these , Zinc, will become the anode and dissolve more rapidly then it would have naturally. The Copper will become the cathode and be protected. There must always be a reaction at each electrode and at the copper it is water being reduced to hydrogen. This is an example of galvanic corrosion and is the basis of Volta's Pile.
Karpen uses noble electrodes but do any of them react ever so slowly? If so, then there is nothing special. If not, then we have a problem (or I need more brushing up in electrochemistry). Surprisingly, platinum is not completely inert as it can build a thin oxide layer and also allow hydrogen to dissolve on its surface, however it is still very noble in acid. We know that water can be turned into its constituents by electrolysis, which requires a fair bit of external energy- but water spontaneously decomposing is unheard of. Sulfuric acid is also extremely stable and will not spontaneously decompose. So what reaction are occuring and providing the current?
4.Tests
So my initial tests will rely on conventional electrochemical techniques. Namely testing each electrode with a potentiostat to determine potentials at which reactions occur and currents involved. These tests are called Tafel plots and you may be interested in googling the term .
If the cell does function, I would like to leave it running a few months and test the acid for gold or platinum. Because of the very low currents, sub milligram quantities of metals corroding can power it for months. This can be calculated by using the formula Q=n(e-)*96500 (faraday's law of electrolysis) Q is coulombs of electricity (amps*seconds). The result of all this should be to determine if gold or platinum are corroding or not.
What happened to the original plan of my suggested Pt/Ag/H2 experiment @pomodoro? It will give superb currents that will rule out corrosion instantly because in this case the disparity of power between inert nitrogen and active H2 is vast. Use platinized plat for the Pt/Au/O2 experiment for maximum current.compare under nitrogen.
Use totaly smooth platinum foil and totaly smooth gold foil in H2SO4 solution,short under air for a few days and chek for pitting in electrodes is another easy method to chek for corrosion in the original karpen setup.chek surfaces under microscope before and after shorting.
Or simply boil a piece plat foil connected to gold foil for a few hours in H2SO4 solution under air and try hasten corrosion.you won't be able to.
@pomodoro, I like your idea of testing the solution for metals, may I suggest that a pile like profitis suggests would only need to be run for a few hours if the test had a sensitivity of ppb, however I think you would also need to scrape the surfaces of the electrodes to test if there was any gold on the platinum, or platinum on the gold.
As to proving it to violate 2LOT, that is step 2.
Violation of 2LOT at very low power production levels is likely impossible as a measurement of temperature depression, however if a plot of ambient heat and power was observed a correlation would be suggested if it is a 2LOT violation. To do this though I think you would have to have the necessary scientific controls as you would need to rule out corrosion rate differentials, thermal gradients, and energy input from extraneous sources, eg RF, vibrations, light.
Therefore given the difficulty of testing for ambient heat driving the cell, what you are doing is the best first step, prove or disprove corrosion at ppb.
He just has to try hasten corrosion by boiling for a few weeks @phil.he won't be able to.
@pomodoro I want to challenge you to try and corrode platinum metal in aquaeous sulfuric acid by boiling.you will fail.
@profitis, I think it is not helpful to in isolation boil some bits of metal in a solution.
Pomodoro's suggestion was to have a working cell producing output for enough time as to have forced on or both of the metals into solution on the basis of the total current flow, if the cell works on the basis of a chemical battery in any way. You believe he will not detect an significant amount of metal in the solution, or on the opposite electrodes, but you cannot prove that simply by suggesting he boils bits of metal.
@profitis, you may well be right and you may have justification for your beliefs, but we all need to take a step by step journey to settle the matter. Might I suggest we (pomodoro, you, me, and the forum) put forward an experimental designed to test all things that will leave us with a conclusion that Karpen is a 2LOT violator, or is not. I feel confident that the forum just seeing that pomodoro and you are doing the basic research has already raised interest in the subject where before it was pointless to and fro.
As I said a few posts ago, funding for the Karpen will happen at the appropriate time, when a few things have been proved to almost everyone's satisfaction. Replication will no doubt happen if pomodoro can deliver proof that there is no corrosion.
That's all fine phil but we want to make sure that pomodoro is not going to bring negative news on purpose.how do we know that he's not sarkeizen or mark E? He must simply prove to us that gold foil or platinum foil will corrode in sulfuric acid solution.in this instance it will be the gold that is suppozed to corrode so he must forcefully try to corrode it chopchop and show us. He must heat it to speed up reaction rate.
@profitis, I must say that your comment was not reasonable, firstly it is patently obvious that he is not Sarkeizen, or MarkE, secondly if he were out to do your subject harm he would simply lie about doing the experiment and report detrimental (to your argument) results. If you want to progress you should have respect for pomodoro and others that engage in practical ways. Pomodoro has chosen of his own free will to do some actual experiments and he should be congratulated, but he does not have to do what you tell him to do.
Taking your suggestion on a purely scientific basis it proves nothing other than the chart that pomodoro posted is correct, clearly Pt and Au should not react in the proposed solution, however the chart does not qualify Karpen cell operation over a long period of time, you say it will not corrode in 60 years, or ever, pomodoro proposed to test that by having such a massive number of electrons transfer across the cell such that if it was ion there would be a predictable concentration of Au or Pt, or both in solution.
My view is that the solution will have traces of metals in it, irrespective of the chart data, simply because water erodes glass, plastic, ceramics, metals etc. The issue is to gently operate a Karpen, and to take solution samples periodically, if the concentration of metals in solution does not rise then you have your first test passed. Boiling metals will 100% for sure dissolve metals, I would predict that if you boil in pure water a gm of Au or Pt for 100 years the metal will be completely dissolved, that is not chemistry, that is to me common sense physics.
@pomodoro, what do you think?
phil I'l bet you my house that platinum or gold will not chemically react with water beyond a few picograms over a period of 100years of boiling in a liter water.the equilibrium constant for reaction of gold or platinum with H+ ions in sulfuric or phosphoric acid solutions is dead fixed on something like 10-15 and is reached in a matter of seconds in a glass of acid. Platinum and gold do not even combust with O2 at red heat.all I'm asking is for mr pomodoro to accelerate the conditions of alleged corrosion in order to rule it out.I'm not panicking I'm just suspicious of reasons for abandoning the agreed upon test.indeed any karpens commercial value will be sized against a normal slow galvanic corrosion in any case.
Calm down everyone, first of all I can't rush these experiments even if I tried. I work, and this is just a lunchtime hobby for me. I haven't read up all there is on Karpen and I don't know these other people's names that have been mentioned.
The Ag/Pt experiment seems interesting, but I don't see any correlation to the Karpen pile. Why introduce hydrogen gas? I'm sure you do get a voltage as you say but that will probably be due to oxidation of hydrogen at one of the electrodes. That's not free energy nor conversion of heat to electricity.
Does Au or Pt corrode in boiling dilute acid? Of course not, not even going to try, but Pt does form an oxide layer and absorbs hydrogen as in the scan below done in 0.5M H2SO4 (from the web). So its not as inert as gold in an electrochemical sense in the same volt range..
Truth is, I don't know what is happening and that's what I want to find out. You may choose to not believe the results, but it wont hurt to pay an electrochemical lab to run the same tests and compare results.
Back to the experiment, I do have sensitive equipment that should detect ppb gold levels, not sure about platinum, but I can always send the sample out to a lab. I also have a balance that can measure down to 0.01mg, but at such low weights its easy to introduce errors.
So for now I have to successfully plate gold on Pt or another electrode and worry about the rest later....one slow step at a time. Keep the ideas coming though, some sound great.
What would combust H2 gas under an atmosphere of pure H2 gas mr pomodoro? Purge the system. You will get much more power density in the H2 system and make it easier to rule out chemical corrosion of the Pt(-) anode.we want to get catalytic hydrogen spillover(google) to power the cell Pt/Ag/NaOH or easier Pt/graphite/NaOH permanently.
Or better yet.do you have any palladium chloride lying around mr pomodoro.plate a platinum foil with palladium black and then you will surge the power density even higher(1-10milliamp/cm2).leave the puny oxygen cells and focus on the potent hydrogen cells.
Quote from: profitis on July 01, 2014, 09:36:01 AM
What would combust H2 gas under an atmosphere of pure H2 gas mr pomodoro? Purge the system. You will get much more power density in the H2 system and make it easier to rule out chemical corrosion of the Pt(-) anode.we want to get catalytic hydrogen spillover(google) to power the cell Pt/Ag/NaOH or easier Pt/graphite/NaOH permanently.
Dear Profitis, as I mentioned before, I would like to concentrate on the original Au/Pt pile for now as the concept of a current being generated between two non reacting metals in an 'inert' electrolyte is amusing.
Now the fact that you understood the word oxidize as the combustion of hydrogen is rather worrying to say the least. In fact the cell you describe looks to me like a discharged form of the popular zinc/silver oxide cell. In your version zinc is replaced by platinum. The silver electrode would normally be silver oxide in a charged cell, which becomes ,as you have, silver when discharged. However, any slight film of oxide or any other reducible silver film will still be able to be reduced.
The hydrogen gas you introduced will adsorb easily on the platinum to make the classical H2/Pt half cell seen in all the text books. Hydrogen gas will be oxidized to H+ (instead of Zinc to Zn 2+ in a standard Zn/Ag2O cell) as any silver oxide or similar silver compound gets reduced.
Sorry butI just cant see anything special here.
Mr pomodoro mr pomodoro...the oxygen catalytic spillover cells are of no commercial interest or scientific value,you saw for yourself the 70year debate still unresolved they are a waste of time.we are begging you to build for us a high-powered hydrogen spillover device that will give permanent power bursts in the milliamp range.you will set this thread on fire if you can do this one favour please (-:. Leave the palladized platinum/Ag under H2 for a day to chemically reduce any surface metal oxides on the silver then pipe in more fresh H2 then seal off totaly.this will totaly rule out any chemical COMBUSTION of H2(I love the word combustion).
@pomodoro you can also attatch a small piece of aluminum foil to both the Pd and Ag when you plunge them into the NaOH to ensure total saturation with H2 and total reduction of surface oxides WHILE piping in a stream of H2.the aluminum will dissolve completely in caustic soda in a matter of 30mins or so.you will see H2 bubbles stream off both electrodes ensuring total reduction of oxides.I'm asking you to build a fuel cell with no oxygen or oxidizers present.
Let me admit from the start that I don't as yet know of these cells and how special they are supposed to be. Perhaps a good brief link with at least a little sound science would be beneficial, but yes , if there is nothing that would reduce with a favorable delta H on the silver or in solution and there are bursts of mAs then I would find that interesting. However the 'free energy' aspect of this cell to me is lost since hydrogen is sure to be reduced at the Pd/Pt anode; the cell is using a fuel which we need to manufacture. Or, is this cell supposed to decompose water at both electrodes, somehow sapping heat from water?
Quote from: profitis on July 01, 2014, 01:20:17 PM
@pomodoro you can also attatch a small piece of aluminum foil to both the Pd and Ag when you plunge them into the NaOH to ensure total saturation with H2 and total reduction of surface oxides WHILE piping in a stream of H2.the aluminum will dissolve completely in caustic soda in a matter of 30mins or so.you will see H2 bubbles stream off both electrodes ensuring total reduction of oxides.I'm asking you to build a fuel cell with no oxygen or oxidizers present.
You are going to oxidize Al with water and you claim that no oxidizers are present???
2 Al + 3 H2O => 3 H2 + 1 Al2O3
@pomodoro it is powered by HYDROGEN SPILLOVER straight from the textbooks my friend.please google.anode:H2 > 2 H(atomic)>2 H+ +2 e. Cathode:2H+ +2 e >2 H(atomic)>H2 in acids and in bases anode: H2>2H + 2OH- > 2H2O + 2e cathode: 2H2O + 2e- > 2OH- + 2H> H2
@markE. The only thing in the cell is pure hydrogen,palladium,silver,caustic soda soln.there are no oxidizers present.aluminum dissloves in seconds,if needed.
@sarkeizen google is saturated with hydrogen spillover,all based on same principal: ficks law of diffusion
Umm I'm not convinced it will run without using up the hydrogen but it shouldn't be too hard to make a tiny version and see how long it supplies current vs a rough estimate of how much h2 was introduced. So what exactly is required? I have pure Ag foil ,plain Pt foil 1.5cm sq but no Pd. I could possibly plate the Pt with Pd but need to check my chemicals. What molarity NaOH and what current + open voltage are expected. Is the output to be taken continuously or pulsed when voltage recovers?
@pomodoro let's look at the big picture: if you seal it properly or just continously stream in hydrogen through a valve what can burn the H2.nothing.zilch.zero. Only textbook catalyst spillover will take place.you said you have already got platinized platinum,thats a good start and will do instead of palladium.make sure that it is pitch black for maximum surface area.take your silver foil and a carbon rod and anodize your silver for a few seconds in NaOH soln to blacken it with Ag2O surface then cathodize it back to Ag until you see H2 bubbles stream.the Ag foil will now have massive surface area and will be grey in colour. Use silver or gold wire on both Pt and Ag as leads out of your spillover device bulb as these metals do not leak H2.you may use copper wire on both for this test but use it thin and try not to get it wet during the final measurements.I'm not sure wether your Pt electrode is naked or encased in glass in which case you will have to stopcock seal adequetly using silicone grease.you cannot afford to have the slightest leak-hole otherwise air gets into our test device. Its highly advantageous if your lab has bottled H2 at hand as opposed to the effort of making your own H2.your Pt should just touch the electrolyte as it must have exposure to H2 and your Ag should be half or fully submerged.use 0.5 to 1M NaOH.
Current should be in the 300micro-2milliamp(or more?) range for a square cm heavily platinized Pt and treated Ag under pure H2. It will be 0.3-0.5 volt at total rest.it will give a quick burst of charge everytime you short it and after the first few bursts it will reach its steady power value which will be its permanent capacity provided no air gets in there.discharge it for a second,allow a few seconds for recharge.discharge it for a minute,allow a few minutes for recharge.its like a self-charging redox cap.
Ok, after the karpen I shall have a look at this sealed hydrogen cell. Please lets focus on Karpen for now and start another thread later on the hydrogen spillover cell.
Back to Karpen and standard electrochem, I have decided to individually test each electrode in 1M Sulfuric acid, in oxygenated and deoxyenated enviroments.
Anodic and cathodic scans will be run about Ecorr just as is done for any corrosion tests.
Initially other metals known to corrode such as Iron and Copper will be tested and the plots compared to the gold and platinum. These Tafel plots will be used in an Evans diagram to show the effect of coupling the Pt to the Au.
The first question I want answered is 'do any of these noble metals actually corrode?' the anodic scan could provide answers. As the metal is forced more positive, and if the current does increase, the electrons must come from some oxidation reaction at the electrode. If the voltage is kept below the oxidation of water to oxygen, then electrons can only be created by the oxidation of the metal.
Does anyone disagree with this, and if so, why exactly?
If we can accomplish something with the hydrogen bomb then this thread and even website takes on a historical event @pomodoro.we will be the first live internet interactive to slamdunk a macroscopic 2lot violation,if you can get hold of palladium chloride we can take this thing into the 2-10 milliamp/cm2 range.your enrique fermi and I'm oppenheimer lol. Ok.. let's slamdunk the smallfry first..an underpotential on Au or Pt foil is going to liberate oxygen gas yes because polarization builds up from infinite nernst dilution of oxygen gas/cm2 on your electrodes up til full saturation of O2 coverage/cm2. So that is no way to look for corrosion which is why I'm suggesting speeding up corrosion on a Pt/Au linked couple by boiling.both Au and Pt are used in the most highly sensitive O2sensors and if corrosion current was an issue for example in seawater then these highly sensitive instruments would have no value for O2 potential calibration.
I want to suggest throwing the gold away and using TWO Pt foils for the present microamp range oxygen karpen tests @pomodoro,what do you say...karpen used identical electrodes in figure 2 from his patent application.
Nor is there any internet info that can show that such spillover is irreversable @sarkeizen.I find that intensely suspicious.you must remember..karpen was also playing with hydrogen cells..open up dogaru and cazacu's referance at the bottom of the wikipedia article on karpen.
Don't know about the chloride I have to ask around, but I have 10%Pd on activated carbon. This stuff is expensive so I don't want to waste it.
Regarding your suggestion of Karpens #2 picture, you propose the upper electrode be half exposed to oxygen , the other submerged in the acid solution or alkali? Any use of any other chemical such as benzene? What about stirring?
Platinized platinum will have to do for our future hydrogen experiment then @pomodoro.if it was platinized by the manufacturer company then it will do fine.if it was platinized by you then alot will depend on your platinizing skills because the platinum black must be totaly adherent and conducting straight onto the underlying foil. Karpen did not use benzene in figure 2. He used one single electrolyte and so did I in my series of tests a few years back.take a solution of sodium hydroxide under air and touch the surface with the bottom end of a PLATINIZED(black) platinum foil.take a aqua regia etched smoothish platinum foil and immerse it totaly under the electrolyte next to your platinized cathode.you will now get perpetual current bursts in the region of 50-100 micro-amps/cm2 if you do this properly. The surface platinized electrode is your cathode(+).the submerged non-platinized foil is your anode(-). this is an oxygen gas concentration cell.the nernst equasion applies.the larger you make your anode and cathode the larger your current.voltage is about 0.1-0.2v
Do not stir the above @pomodoro.we don't want people to say stirring powers the cell.leave the cell dead still once sealed.use platinum wire as your leads out the cell.
Ah OK now I understand. You believe karpen's cell woks because the pt concentrates oxygen from air, due to its nature, and the gold does not, thus a concentration cell is formed. So, if I have a working model in air and put it under vacuum absolutely no current would flow, correct?
If you put any of the karpens under nitrogen then very negligible current will flow.you have to make sure of no dissolved oxygen if you try this.karpen himself put them under argon and showed grossly negligible current compared to oxygen OR hydrogen atmospheres.catalytic SPILLOVER (google) will only happen with actively chemisorbed (google)gases.
I'll devote some time from wed next week constructing one of these cells and test the voltage & current in O2, Ar, and H2 atmospheres. I'm still going to check gold as well, want to check its potential vs pt in deoxygenated dil sulfuric.
Exellent mr pomodoro.we can make history right here right now,the path is clear.we have only one thing to prove: that textbook catalyst spillover can be totaly spontaneously reversable.
Mr profitis , for the top electrode of your requested test with hydrogen, the expected EH at 25C is 0-0.059log(pH21/2/[H+]) which satd. with H2 would have p=1, but the distant electrode has p=0, any idea of the potential there before any hydrogen reaches it?
The Ag electrode will have a voltage less than the standard on platinized platinum 0.828V in 1M OH- ion solution mr pomodoro. Probably around 0.2V for the silver electrode directly due to hydrogen galvanic OVERPOTENTIAL on an Ag hydrogen electrode.
Yep, makes sense, I just found an interesting paper http://pubs.acs.org/doi/abs/10.1021/j150543a032 (http://pubs.acs.org/doi/abs/10.1021/j150543a032)regarding some H overpotential studies in NaOH, it even used platinized Pt as a reference. I should be able to get the full article on wednesday, to keep as a reference as my tests progress.
Exellent find.I'm toying with a decision to reveal the chinese papers on overpotentials over here in which they compared smooth platinum to platinized platinum for hydrogen but I don't think I should put it here because it might give tangent ideas away.they also compared smooth gold to black platinum under H2 and got volages in the 0.3-0.5v range on a permanent basis.voltages would fluctuate around +- 0.05v like an ordinary batterys voltage fluctuates depending on the days temperature and in accord with nernst equation.the guys(hardcore research institute scientists) were shocked and wondered out loud if certain other claimed 2lot violators round the globe (in the 80's) were in fact real.
Its important to note that there's a line between a concentration cell and a spillover cell eg. I can take two exact same Pt smooth or black foils and put them in the setup and get a strictly nernstian voltage.if we take two different inert metals then it becomes a more spillover-induced voltage for reasons other than concentration and more towards overpotential.
Mr profitus, surely simple cells like these would have been tested for abnormal behavior worth exploiting by now?
I was thinking the same thing mr pomodoro.either their research ended in stalemate due to cost/benefit ratio or their research continued,deep underground.perhaps things have been shelved I don't know.catalyst spillover is also a recently discovered phenomena so the connection would have been made very recently or not at all.nontheless we can take credit for this with a few simple experiments.
We can take this from a strictly overpotential difference point of view without causing too much of a stir mr pomodoro.I'm going to refrain from blowing the anti-2lot horn from now on and be strictly going by the textbook.
Guess I'll have to try Hg as well then?
You know it (-: ...try Hg/Ag amalg
@sarkeizen.gona make your dreams come true,by the textbook.
Ok, started to dig around to see what I've got. So far I have a few shiny Pt electrodes,( platenized Pt electrodes I had are misplaced but if I cant find them in a day or two I can break a specially constructed conductivity cell to get new ones), pure silver electrode, new glassy carbon electrode, plenty of Hg, Gold ~200mg which I precicipated from a weak cyanide solution with dithionite. I'm hoping to make it into a plating solution, otherwise will need to buy some 24k gold and make an electrode out of it. I've got some palladium chloride but in solution. I've got UHP hydrogen, Ar and oxygen.
Since the gold will take a while to sort out, I'll probably start on the Pt/Ag. He are a few questions to save me some work and prove your concept quicky mr profitus.
Note, electrodes are flat, about 1cmx1cm , water is milliQ quality, deoxygenated. Room temp approx 25C. Ag will be pre treated as you described, Pt trated in strong Hcl, then both will be made cathodes in a separate alkaline solution to reduce any surface oxides
1.What conc. KOH or NaOH is preferable.
2.What distance between electrodes?
3.If I use the shiny Pt, will it work and what pre-treatment is needed.
4.Any stirring or keep static.
5.If I saturate liquid with H2 , leave just a few mL of H2 gas above surface and seal it then connect it to a galvanometer , do you expect it to provide a constant current?
6.How long would the current last?
7.Do you expect any dissolution of the silver?
8. Do you expect any silver oxide?
9.Do you expect the hydrogen to be consumed?
The way to judge a success in this instance will be to short-circuit the device for a few hours,disconnect,let re-equilibrate for an hour or so then measure if voltage climbed back up.a resting voltage that falls down to 0.1 with little or no current in its burst-discharge curve or less is a fail and has either a leak or is insufficiently saturated in H2. 1) KOH or NaOH will do fine in 1M conc. 2) put electrodes close-ish for max current,a cm or two apart.3) shiny Pt anodes are useless,you must use use black Pt.smash that conductivity cell carefully(I did,no regrets) 4) DO NOT STIR ANYTHING) 5) a few ml space for H2 is fine.we want to rid the device of as much air as possible.if you can pipe in H2 through the device periodicly or continuously slowly it is best.6) currents are in bursts,depending how much is drawn,you can leak a small steady current at the same or less rate than recharge rate.it depends on how much surface area you crammed into electrodes. 7) not in KOH or in NaOH under H2 no ways. 8) cathodize the Ag and Pt seperately in the device itself if you can using a Pt wire prong with nice big current through it.remove the wire and immediately begin piping H2 through.I used to just dump Al foil into the device to generate H2 and push air out but you must then use fairly con NaOH otherwise it takes too long.if you attatch Al foil to the electrodes its even better for reduction of oxides plus saturation of Pt.
I forgot your question number 9 mr pomodoro: this is impossible unless 1)the device is leaking(air will be sucked in).2) too much air was trapped in the device when sealed,creates a vaccuum and may pop a hole in the weakest part of the device container.3) Ag was insufficiently reduced to Ag metal prior to experiment.piping H2 through the device slowly,periodicly and out a small rubber or plastic valve is best option for those who have H2 lying around in cylinders.be sure to leak it out outside or the next time you light a cigarette will be your last.
At its very best.for a highly blackened Pt anode and Ag cathode and totaly leak-proof system you can expect up to 6milliamps or more/cm2 in bursts of a few seconds inbetween mr pomodoro.
I prefer not to have aluminate in solution. Now, I think the cell may work as follows. Pt black absorbs H2 and concentrates it. A concentration cell is formed, causing Ag to produce H2. As H2 builds up, voltage and current drop. When disconnected, H2 from Ag floats back up and voltage rises again, ready to repeat cycle. I can't see any need for catalytic spillover!
Lol but thats also catalytic spillover.its repeatable.carbon is the usual substrate for spillover.
Aluminate is totaly inert much like silicate but it can give problems if it happens to crystallize out of solution on the electrodes impeding gas access.if the NaOH sol volume is large enough and at right concentration it won't crystallize.
And your PdCl2 solution can be very handy later on mr pomodoro (-: you can also leach Pd out of 10% Pd/C using aqua-reg.
If I have some time I'll send photos of the proposed setup. Once we agree on a foolproof cell I will proceed. I was thinking of bonding the Pd on C to a pt electrode with silver loaded epoxy if these initial experiments go well.
I was going to ask you about photos,that would add some spice to this thread for sure.don't bother epoxying anything mr pomodoro its going to have to be a tight adhering electroplate of Pd black.I used to burn conc PtCl2 syrup directly ontop Pt foil and it would decompose into the most beautiful grey sponge coat.I'm not sure if we can do this with PdCI2 but we can definitely do it with ammonium palladium chloride (this is how they prepare industrial catalysts) I just have to google quick to double-check on the decomposition products of PdCI2
PdCI2 decomposes to Pd sponge and Cl2 gas at 650 degrees C so a bunsen flame should be able to do it.ammonium chloropalladate precipitated from PdCI2 soln and a few drops ammonia soln melts then decomposes directly to sponge at low temp,300degrees
You may proceed with the platinized Pt foil from the conductivity cell meantime and the treated Ag mr pomodoro.it will not fail you.leakage is the only concern and if H2 is piped through periodicly we can eliminate that completely.you can seal when the behaviour is as expected.we want the maximum power from overpotential differences that's all.
Good news. I have small amounts of ammonium tetrachloropalladate, potassium hexachloropalladate,PdCl2 and 1.5 cm of PD wire about 1mm diameter. I also have some ammoniumtetrachloroplatinate,chloroplatinic acid and gold chloride. So think carefully of the best cell we can possibly have first up!
Here is what I plan to build. It should keep the h2 in permanently don't you think? Others reading don't be shy and make any comments.
Here's the ideal for keeping out air mr pomodoro.this ensures continuous dilution and purging of traces of air.the electrolyte on the bottom,away from wire leads,hydrogen gas pumped through the tubes once or twice/day and clamped shut(clamp in this pic),the one pipe remaining attatched to H2 supply cylinder..you cannot use candle-type wax for sealing its very weak and breaks if a vaccuum is formed and it reacts with NaOH making soap which will poison our catalysts.hardcore silicone is best.I melt the rims of this plastic pill container with a cigarette lighter to seal totaly.I melt around the wires enough to seal. What metal are your lead wires made of pomodoro??
Your setup will work for a few days but it won't be a permanent seal.oxygen in the air will be sucked in through the electrolyte via diffusion and it does this with quite a lot of force.is your flask-neck rough glass or smooth? What is that large metal disk in your pic?
OK, I will listen and do an initial test first, with H2 slowly passed on top of the solution after an initial saturation If it works I will find a glass blower to melt Pt wire to glass as leads with a top section that can be melted later to seal permanently.
Problem would be joining the Pt lead to the Ag wire. Will solder last for years?
The large disk is pure silver. I thought of cutting it to shape, with a skinny section as wire. I could solder it to Pt wire but again, I'm not sure about the solder...
I also have kilos of triple distilled Hg. Would this not be better than Ag? It can sit at the bottom of the cell with the tip of a Pt wire encased in glass touching it- I havent checked if it amalgamates so that could be a problem too.. Doesn't it have a much higher overpotential?
I don't have all that many hours to work on this so would like to get something going that's pretty good.
Do my setup above for now as a preliminary yes pomodoro.seal around the pipe entrances with harcore silicone. You must have minimum exposure of silver wire to the electrolyte on the anode side otherwise slow self discharge will take place there and reduce voltage.use smooth silver wire leads.you don't have to solder just twist properly(many twists) onto the anode Pt wire,no corrosion will take place as it is actually the Pt wire which is anodic.do not cut silver from the disk to use as wire use proper wire.gold wire is also fine.you can use the below v-setup using a single bent glass tube or polyethylene tube.I'm using a drinking straw in the pic just to illustrate.the v-setup allows to easily melt both ends shut one at a time.electrolyte is inserted via syringe when Pt side is melted shut then electrolysis gives H2 there and oxygen generated on the other open end with Pt wire prong and ejected.a tiny bit of air will be trapped when you seal cathode side but not enough to recombine all the H2.a slight vaccuum will form after sealing.the tube can also be wider on the Pt side for more space for H2.
Don't use mercury now as it has small surface area as you know.cathode surface area is equally important as anode area for power current.we will have to amalgamate with silver later on and then anodize-cathodize same treatment as for the silver for area.your platinized foil looks well worn I see a lot of its black has fallen off but it should do fine.clean it in nitric,rinse thoroughly.
You can use bare copper wire for the initial test but it must be far above the electrolyte.copper wire won't leak H2 out the device but it will corrode if wetted at the interwire connections.
Thanks for all the ideas, you have given me plenty of info. Now its my turn to get something done. Next post will have some results, keep checking folks. Oh that pt is not platinized. I will try the palladizing treatment first.
Please try electrolytic palladium deposition by the book first to be on the safe side pomodoro.I think its done much the same way as platinum deposition.swirl a few drops HCl in with the potassium chloropalladate solution and add a tiny bit lead acetate or chloride and deposit with small current.use graphite as your anode.etch your foil prior to deposition.palladium swells slightly when it takes in H2 so it must be adherent.google deposition methods to find out more.heat for a few mins in dil.HNO3 afterward to clean out any deposited Pb(lead)
If you can smash that conductivity cell and retrieve that platinized foil I would feel less nervous @pomodoro.the first test that we show here must be good.
Use tiktak presstick around H2 pipe entrances into the device instead of silicone pomodoro.if silicone peels from movement there will be problems.use lab clamp-stands to prevent movement of pipe inlets.test the device container for leaks under washbasin water before assembly,syringe in some conc NaOH and aluminum pieces INSIDE the shell through inlet holes to generate gas and press your fingers over the two gas entry/exit-holes..gas must only escape under your fingers NOT at the rims or through the wires.you will spot a leak under water.we want robustness. Syringe out or siphon out the waste and rinse
Been busy last few days but managed to prepare the palladium sponge. The photos show the Pt electrode in aqua regia (it was still shiny after the 3 minutes), plating of Pd (followed a method from journal with no lead acetate), and the cathodic electrolysis of 1M NaOH over weekend at 60mA to test adhesion. I've made some AgCN in order to plate the other similar Pt electrode with Ag for the test. I don't have silver wire and it will be easy to check the plate during the oxidizing step.
The pics
https://flic.kr/p/ofvygG
https://flic.kr/p/ohfRxi
https://flic.kr/p/o13oyf
https://flic.kr/p/ohfSNV
https://flic.kr/p/ohmDhN
Abandon any attempts to plate Ag onto Pt pomodoro.H2 will creep into the Pt below and swelling forces will pit any coating.any holes in the coat will drop our voltage so don't do this.take a piece 925 jewellery silver( or old silver coin.thers hundreds),etch it in HNO3 to roughen surface and leach out surface Cu(0.75%) followed by anodizing-cathodizing in NaOH sol.I've always used jewellry silver with great success and it looks like in the pic below after treatment. I'm impressed with your palladium coating it looks fab.aqua-regia only begins to etch plat after boiling for at least ten mins I forgot to tell you.
If you don't have silver or gold wire then you must do with copper wire.its ok to wet copper interwire connections during preparation setup but during any measurements the interwire joints must be far above electrolyte.cut your silver disk into a long section so that its far above electrolyte.twist copper hectictly tight onto leads otherwise corrosion will disengage electrical conductivity.use scrap jewelly silver,a bangle,a coin,a large earing,a bracelet,for the cathode material or your silver disk,do not plate Ag onto anything.
Is silver solder any good profitis? If I do as you say for the copper wire the silver will stick out into the h2 unlike the patent. Heat shrink tubing should resist the solution at room temp. So if I silver plate other metals instead ( copper nickel) its no good?
Plate onto glassy carbon or graphite rod if you must pomodoro.at least then we won't have to worry about pitting so much even if it does happen.plate thickish then anodize-cathodize.what happened to your silver disk? Why don't you want to use it?
I don't know the composition of silver solder so I can't say if its ok.we must eliminate all unknowns pomodoro.
If shiny part of silver sticks out electrolyte its no prob pomodoro.as long as black part submerged.it doesn't really matter even if part of the black is exposed to H2 because its overpotential remains quite invariant.this is the nice thing about spillover cells.you can shake em,kick em,even hold em upside down in wet electrolyte and they work fine.in nearly all of my experiments the black part of the Ag was partially exposed to H2 atmosphere and it didn't cause reduction of overpotential difference.H2 gas diffuses straight through electrolyte
@sarkeizen....watch...
@mark E yes ofcourse entropy increases with time here.do you not think that concentration cells belong to the universe?I'm going to tell you what your favourite(and my favourite) textbook wikipedia told me: electrochemical entropy takes precidence over temperature entropy.gravblock is correct,'entropy is the ultimate order'
@mark E..the electrochemical entropy chops a temperature gradient into the ambient until equilibrium. disengagement of switch throws system back into temperature entropy's hands and disperses any gas away from cathode.two interswitchable entropy states.
Quote from: profitis on July 13, 2014, 10:23:14 PM
@mark E..the electrochemical entropy chops a temperature gradient into the ambient until equilibrium. disengagement of switch throws system back into temperature entropy's hands and disperses any gas away from cathode.two interswitchable entropy states.
LOL! It's always amusing when you decide to regress into incomprehensible grammar. Perhaps you would like to state in plain English what you mean by: "entropy chops a temperature gradient into the ambient", or "disengagement of switch throws system back into temperature entropy's hands".
Quote from: profitis on July 13, 2014, 04:54:46 AM
@mark E yes ofcourse entropy increases with time here.do you not think that concentration cells belong to the universe?I'm going to tell you what your favourite(and my favourite) textbook wikipedia told me: electrochemical entropy takes precidence over temperature entropy.gravblock is correct,'entropy is the ultimate order'
Really? You are going to go with "entropy is the ultimate order"??? Entropy dear boy is a measure of how dispersed energy is. Saying as you have that: "entropy is the ulimate order" is like saying "Length is the ultimate size." It makes no sense.
Quote from: MarkE on July 13, 2014, 10:59:54 PM
Really? You are going to go with "entropy is the ultimate order" ??? Entropy dear boy is a measure of how dispersed energy is. Saying as you have that: "entropy is the ulimate order" is like saying "Length is the ultimate size." It makes no sense.
MarkE,
Does a reversible chemical reaction proceed in both directions?Gravock
Quote from: gravityblock on July 14, 2014, 12:04:39 AM
MarkE,
Does a reversible chemical reaction proceed in both directions?
Gravock
Now you are spamming.
Quote from: MarkE on July 14, 2014, 01:39:57 AM
Now you are spamming.
You are grasping for straws! Answer the question MarkE!
Gravock
Good news profitis, I now have a silver electrode. I did a few CVs of the Pd, Pt and Ag in 1MKOH under N2. You can see the overvoltage required on the Ag for yourself. Voltages are vs Ag/AgCl.
When I finished the scans I connected the Ag and Pd together. The current jumped from a few mA very quickly to uA and then to zero. No galvanic corrosion going on under N2. Recovery was very poor when disconnected.
Exellent pomodoro we are getting closer to the manhatten test,the big one.can you post a closeup pic of the silver cathode that we are going to use in the gadget please.I would like to see its surface state before assembly.
No problem. That photo was taken before the anodic etching and subsequent reduction. During the anodic scan, not shown here, there is an awesome moment when it turns black almost instantly.
Btw,I noticed that although the cell voltage was zero when discharged, it immediately improved back to about 300 mV when the electrode was moved to another place. I assume this to be due to concentration gradients in the unstirred electrolyte.
For the big test #1 H2 will be bubbled in the KOH then allowed to flow on top. You want me to then measure the open voltage, short the cell to monitor the current flow until it levels off and then remove the short and see how long it takes to polarize again. Is that correct? Tell me how you would run the setup exactly
@mark E.no.electrochemical entropy compresses gas onto the cathode in order to equilize potential,at the expense of temperature entropy.as simple as that.if there was no communication of gas between anode and cathode then you will see pressure differential buildup exactly equivalent to voltage difference.
It could very well be that when you moved electrodes in the nitrogen test that you were disengaging O2 and H2 microbubbles off the electrodes pomodoro,shock of all shocks lol,spontaneous electrolysis.when the gadget is ready for firing,short it for about 30mins,then let it rest for 30mins,then take that voltage reading,then short for 1 min,rest for 30 mins,take reading,short for 1min,rest for 30mins,take reading so on and so on.play with it pomodoro,also take current reading shot at TOP of discharge curve.some meters can freeze-shot these measurements I don't know what electrical measurement system you have but for standard multi- meters this will do fine.play with it,try to annihilate its voltage permanently.
Here's the math pomodoro: E(gadget)= RT/nF ln kf1/kb1 - RT/nF ln kf2/kb2 where k is the rate constant of forward and backward reactions at each electrode at rest for H2 + 2OH- >< 2H2O + 2e-.note that k is a constant dependant on electrode material,it is set.
Try to get hold of an analogue meter in the range 0-1 milliamp or micro-amp meter in the 0-500 range so that we can slamdunk it to visibly impress viewers with its power pomodoro.it should give the sound of the slamdunk aswell.ofcourse this depends on how much power we get from the gadget.
OK, pics of the setup, as well as the eletrode are shown below. Setup in not complete and still requires some rubber bungs. Setup includes 1x1012 ohm millivoltmeter, which I just checked against Cu/1M CuSO4 //Ag/AgCl. Got +111mV @19C, old school multimeter with 50uA minimum FSD, 3 neck borosilicate flask and Ag/AgCl electrode for measurements.
Nice rig.
And there it is,the gadget,beautiful,breathtaking.is the tip of that Ag-AgCl electrode our Ag electrode pomodoro?? How did you seal the fit through the top of the borosilicate flask?
That multimeter is perfect for showing a slamdunk and we can do it without breaking it,we just have to measure the gadgets current at full power then scale the meter to 20% of gadgets full power.
Quote from: profitis on July 15, 2014, 05:17:36 AM
And there it is,the gadget,beautiful,breathtaking.is the tip of that Ag-AgCl electrode our Ag electrode pomodoro?? How did you seal the fit through the top of the borosilicate flask?
Yes that is the Ag electrode. On the box it said metallic electrode. Dates back to at least the 70's I think, a company called titron made it.
As mentioned, the gadget is not quite ready. I plan to use ground glass quickfit fittings where I can, rubber where I can't. I found a cylinder of hydrogen so will try to hook it up tomorrow to slam dunk the needle! I'll take a video of the event, good or bad!
Exquisite pomodoro.if you've got some type of silicone grease lying around to coat all fittings before you squeeze them in place it'l help gaurd against air sucction.I'm very paranoid about air leaks because I've seen the force with which that anode wants to combine H2 in air.I've had holes vaccuum-punctured through thick plastics in experiments after sealing due to air being left in containers.what we are doing now with the gadget is best ie.flowthrough purging.holding thumbs for the test here..
No need to worry about leaks profitus , H2 will be passed constantly on top of the electrolyte for this test. If it works, next one will be sealed, but in another, smaller and better suited setup.
PS I think the secret is in the that huge positive current peak you see in the Pd cyclic voltammetry. When the adsorbed H does this: H -> H+ +e- (or the more correct alkaline expression) , as the voltage is forced in the anodic direction but still very negative at about -0.7V (vs Ag/AgCl).
Basically, H2 was generated at the very cathodic potential and much collected on the Pd. It was forced off as the scan reversed direction. A peak of 37mA is discharged! It depends on the scan rate, but the coulombs will be the same regardless of the rate. Compare with the Ag scan, nothing at all happens in the reverse direction. No H2 was captured by the metal.
In the gadget, H2 in the electrolyte will be collected by the Pd and oxidized 'discharged' if the Ag /H2 can bring it more anodic than the -0.7 V. It will be interesting to measure the individual electrode potentials just before shorting, and the shorted potential as well, vs Ag/AgCl.
If it works and the Ag side reduces water, to H2 then we are in business professor!
Adsorbed H2 will be oxidized at the anode,water reduced at cathode even at 0.01v overpotential difference pomodoro so long as there is overpotential difference.this is what brings certainty to the whole class of cells of this type.its really only a matter of current that gives the thing power and potential commercial viability.I've seen voltages peak at 1.1 under pure H2 before at maximum saturation this is why its important to get all the parameters and info sorted before sealing.these cells behave much like a compressed spring,quick to discharge,slower to recharge it depends on the materials.you can split-second-touch-discharge it on that meter with a few seconds in between to show its power impressively continuously.buisness is not the word pomodoro,history is the word for gadget if all goes smooth.this is the first time in history that a H2 powered karpen will be broadcast live and along with it a macro- kelvin law discrepency to boot.holy shit what are we doing lol!
Some Artwork:
Gentlemen the gadget has been tested.....
Check out the preliminary results on youtube.
http://youtu.be/JpVPrLw9e04 (http://youtu.be/JpVPrLw9e04)
The cell utilizes palladized platinum on the left and a silver electrode on the right.
Hydrogen gas is bubbled through the 1 molar potassium hydroxide solution.
The high impedance millivolt meter displays the emf between electrodes. It stabilized at about -900mV. The minus meaning that the Pd/Pt was more negative. When shorted through the multimeter, a current in the milliamp range resulted, but for a short time, and then stabilized in the range of tens of uA. Please note that the meter was found to be not all that accurate later, but be assured that milliamps are initially discharged, as I later slamdunked a 1mA meter with ease.
By monitoring individual voltages I also discovered that it is only the silver electrode that depolarizes the discharge. The Pd/Pt voltage hardly falters during discharge.
The more negative potential on the Pd/Pt indicates that oxidation occurs there, and it is unlikely that any silver gets oxidized during the discharge.
Please discuss or the experiments will end...
Nice set-up and work!
So, from what I can tell electrically: The cell maxed out at 955mV terminal voltage with an effective open circuit load, discharged to a couple hundred mV when shorted through the 2K or so of the meter , and then slowly recovered back towards 955mV after the load was removed. My very simple equivalent circuit model of that behavior is below.
R1 is much larger than R2. If maybe you had some banana jumpers and clips we could see the terminal voltage when connected to the mA meter so as to estimate R2. Then we could use the recovery curve to estimate the R1*C time constant. If the timing were well monitored along with the terminal voltage values I think we could derive pretty good estimate for: R1, R2, and C.
Dammit I can't get the vid on my blackberry to open.can you put the vid up over here on the forum pomodoro or onto tubidy.com or I'm going to have to wait until I get to internet cafe.so what does this mean pomodoro.was the experiment successful? Where is the voltage now.what is the current at top of discharge curve now.did you let it rest.
Cheers.
Umm I didn't check the meter's impedance. I assumed it was closer to just a few ohms as it was in current measurement mode. I also tried a digital meter with similar results. The time to recover to 912mv was 5 minutes.
The voltage recover each time and much more quickly if the hydrogen is bubbled furiously. It still recovers with h2 passed on top only, but slowly.
When it was nearly equilibrated at -906mv the Pt measured -997 and the Ag -83 . Take away the 190 mv from the ref electrode and you get -800 mv which matches the expected potential at pH 14. Shorting the electrodes makes the Ag polarize to the Pt electrode potential, current flows. 30 uA in one test was continuously flowing after the discharge.
And the current bursts are definitely in the milliamp range inbetween decent rest correct pomodoro?
I was expecting voltage in the 0.5-0.9 range so this is very good news to be at around 0.8
mA for sure. Another secret electrode I tried gave less volts but tens of mA and continuous mA for a minute!
Lol you know it,there's too many secrets.the gadget test is smelling like a whopping success pomodoro its our names that go down in history today 16th july 2014.leave the gadget on slow-suface gas flow overnight and measure its voltage and freeze-shot its current with a digimeter at top of curve first thing tomorrow.it must withstand the test of time now but so far total success.trickle a minute amount gas(just enough to displace any air that gets in there) oversurface overnight.do not dismantle the gadget just yet.
I'm not at work now but will do that tomorrow and day after. So you want me to discharge through say 100 ohms and record it on an oscilloscope? I don't have a digital recording meter.
I suggest a 1K to 10K Ohm load. uA meter movements are often close to 2K Ohms. mA movements are lower: 10's of Ohms typically.
I'll give 10k a go and video the decay.
Great!
Try get hold of one of these meters for the top-curve current freeze-frame measurement pomodoro.steal one,borrow one,buy one if you have to,they are cheap here in sa so they must be cheap there by you.oscilloscope will confuse viewers who are not aquainted with it.
That looks like a cheap < $10. DMM.
The idea of the scope is to set it to a slow sweep and show readings over time like a strip chart recorder would show. It sounds like a perfectly good way to show the terminal voltage versus time to me. It will be especially good if the scope also displays the measured voltage. The only limitation will be the finite quantization of generally 8 bits.
Scope and regular digi would be great @mark E.the nice thing about the digi is it freeze-frames the first current surge reading it gets.10$ is spot on yes.
Be sure to measure the voltage before you measure current tomorrow pomodoro and not other way round.we want to see its true resting potential.
Ok resting potential is 947mV.
Check out the pdf with the oscilloscope traces of discharges and recovery time.
Great! It definitely looks like there are two time constants at work. Was the unloaded condition into:
1) Open circuit across a X1 1 MegOhm probe?
2) Open circuit across a X10 10 MegOhm probe?
3) Across a 10K resistor into a X1 1 MegOhm probe?
4) Across a 10K resistor into a X10 10 MegOhm probe?
Unloaded is into 10M probe+10^12 ohm meter
OK here is a pdf of the silver vs the 'secret' electrode.
Quote from: pomodoro on July 17, 2014, 01:28:22 AM
Unloaded is into 10M probe+10^12 ohm meter
OK here is a pdf of the silver vs the 'secret' electrode.
Thanks.
Excellent pomodoro the manhatten test not only matched expectations but exceeded them too.6mA! Are you saying there was around 6mA/cm2 at the top of curve from the gadget pomodoro?
3mA/cm2, the Pt has 2 faces. , but I think the Ag area is the limiting factor.
Here is the latest test, I'll know the results tomorrow, then I need to take a break for a while..
https://www.youtube.com/watch?v=6b4Bgbj95lA
Nice. Thanks for all the work that you have done.
Right yes.now imagine what a cm3 is going to do.that first scopeshot illustrates clearly the selfcharging capabilities of the gadget.take a rest pomodoro we need to discuss things
I'm glad that we staked the historical claim otherwise somebody else was going to do it sooner or later.
Quote from: profitis on July 17, 2014, 05:01:35 AM
Right yes.now imagine what a cm3 is going to do.that first scopeshot illustrates clearly the selfcharging capabilities of the gadget.take a rest pomodoro we need to discuss things
It shows that a cell that is continuously supplied with feed stock repolarizes after being loaded down. The tests with the "secret electrode" should give you pause. Do they simply reflect in an accelerated time frame what is going to happen with the Ag electrode?
Lol so tell us what's going to be 'usedup' in a sealed system then mark E.its a karpen cell,how long do you expect it to last?
If I knew what the dud electrode material was then I could tell you straight why it failed
The secret electrode was graphite
Quote from: profitis on July 17, 2014, 05:30:14 AM
Lol so tell us what's going to be 'usedup' in a sealed system then mark E.its a karpen cell,how long do you expect it to last?
You claim to be an electrochemist? Really? You have a cell, feed stock in the form of hydrogen is continuously admitted to the cell during the experiment and you assert that the system is closed? Really?
The experiment makes no attempt to assay materials after it has run. As an alleged practicing professional, on what basis do you claim that there is evidence that oxidation / reduction did not take place within the cell? Or alternatively that electrons could move through the external circuit without oxidation/reduction taking place in the cell? What do you claim that pomodoro's very nice experiment shows that is out of the ordinary?
Quote from: pomodoro on July 17, 2014, 06:14:57 AM
The secret electrode was graphite
I would have incorrectly guessed some metal that is quick to develop an oxide layer like Cu or Al shutting down the reaction.
Uhhmm,nah try it markE.its just reversible spillover.it'l last past that expiry date.
Yes only you wouldve guessed Al mark E.we was taught in high school that Al dissolves in NaOH sol.the power wouldve been monstrous and steady if it were Al.
You shoulve kept the graphite experiment going pomodoro,that current was ready to switch polarity lol.but it wouldve been weak anyway.
Yesterday, the graphite was giving many 10's or peak mA and a constant current of 2mA when shorted through the meter. Quite impressive. However, I recall that I was bubbling the hydrogen constantly, not diverting it to the top of the flask after having saturated the solution.
Today, I cathodized it in a separate KOH beaker, with a Pt counter electrode and a power supply, just to clean it with fresh H2 bubbles.
When I dipped it in the cell and waited a while, a whopping 1.2V developed. WOW I thought , but as you saw each time it was used it never recovered. I'm not sure but I guess it cant sponge up the hydrogen from the solution very well.
I also tried palladized silver. Again excellent fresh from the beaker, but quickly died down as well.
Same thing for shiny platinum, got zero volts real fast.
I still need to try lead,nickel,copper and a few others.
So Mr Profitus, I must admit that you did come up with a system that seems to work well at this stage of the research! well done!!!
Back to the basics, everyone, lets start from step 1.
1. Why alkaline and not acid as used by Kapern? I realize it lowers the E of the H/H2O couple - well it did as Nernst would have predicted at the Pt, from 0 to -800mV. I dont know about the shift at the Silver.
2. The Pd/Pt voltage is very rock steady when discharging, no wonder a similar electrode is used as the zero volt standard. The 1cm square has in reality a much larger surface area.
3. The silver is another story. What formula exactly can be used to predict the voltage that I would expect there? Is it the same as the platinum plus the hydrogen overpotential on silver? I need to read the paper on the studies of this overpotential, but I did not think it was as huge as 0.9V. Even the CV scans I did did not show such a massive difference in the cathodic scans.
4. Why does the silver electrode look more like a capacitor , being charged up by the Pt/Pd when they are connected, which then slowly discharges upon disconnection?
Graphite is useless as a H2 sponge,it has monster overpotential.you can replace Ag with graphite as cathode in the gadget. Palladized silver will self-discharge it can't be used,that's why I'm against plating of anything. 1) the electrolyte has nothing to do with overpotential difference in the same cell its just to carry charge.eg phosphoric acid works fine instead of sulfuric in karpens original.as long as there's no corrosion current its ok. 2) yes but its all crammed onto 1cm2. 3) the cv scans only tell some of the picture not all of it which is why I wasn't too interested in them.overpotentialdifference is all that matters.there's no real way of predicting overpotential so they make lists for us. pt was just chosen as our standard. 4)H atoms are very unstable on Ag,recombining quite fast during rest.
I've already given a description of a nickel cell here pomodoro,what do you think,should we collect the prize and split it? Harti wants 1 watt I believe
Now need to put ag sponge on the silver. Oh it was the silver I replaced, I kept the PD/pt for all tests.
Quote from: pomodoro on July 17, 2014, 07:48:37 AM
Yesterday, the graphite was giving many 10's or peak mA and a constant current of 2mA when shorted through the meter. Quite impressive. However, I recall that I was bubbling the hydrogen constantly, not diverting it to the top of the flask after having saturated the solution.
Today, I cathodized it in a separate KOH beaker, with a Pt counter electrode and a power supply, just to clean it with fresh H2 bubbles.
When I dipped it in the cell and waited a while, a whopping 1.2V developed. WOW I thought , but as you saw each time it was used it never recovered. I'm not sure but I guess it cant sponge up the hydrogen from the solution very well.
I also tried palladized silver. Again excellent fresh from the beaker, but quickly died down as well.
Same thing for shiny platinum, got zero volts real fast.
I still need to try lead,nickel,copper and a few others.
So Mr Profitus, I must admit that you did come up with a system that seems to work well at this stage of the research! well done!!!
Back to the basics, everyone, lets start from step 1.
1. Why alkaline and not acid as used by Kapern? I realize it lowers the E of the H/H2O couple - well it did as Nernst would have predicted at the Pt, from 0 to -800mV. I dont know about the shift at the Silver.
2. The Pd/Pt voltage is very rock steady when discharging, no wonder a similar electrode is used as the zero volt standard. The 1cm square has in reality a much larger surface area.
3. The silver is another story. What formula exactly can be used to predict the voltage that I would expect there? Is it the same as the platinum plus the hydrogen overpotential on silver? I need to read the paper on the studies of this overpotential, but I did not think it was as huge as 0.9V. Even the CV scans I did did not show such a massive difference in the cathodic scans.
4. Why does the silver electrode look more like a capacitor , being charged up by the Pt/Pd when they are connected, which then slowly discharges upon disconnection?
A capacitor effect suggests to me that a dielectric layer is forming at the surface of one or both electrodes.
Anodize-cathodize the Ag in Na2CO3 sol for spongey pomodoro.you are going to double or triple power out.I wonder what rhodium anode would do???
Did you try the gadgets anode with a graphite cathode pomodoro.what happened.
Congratulations profitus and pomodoro. I am very impressed with the accuracy
of both your exploits. One thing you should do is go for one completely sealed
cell with maximum "staying power". It's hard for the general public to accept
that flowthrough method is not supplying hydrogen "fuel" to the reaction, plus
it is a waste of hydrogen gas.
On the you-tube videos of the real Karpens pile in Eastern Europe from pomodoro's
you-tube home page. I was negatively impressed by the poor quality of the seals on
the real Karpens cells. I was somewhat shocked that they don't appear to have used
frit glass seals on the original Karpens cell. I wondering if we could eventually
expect to see oxygen leakage and cell malfunction on the Karpens Piles because
of this? Also they had a picture of a depolarization mechanism that looked inactive.
I hope this is a filmarker's flaw of taking a picture of a disconnected device or
a secondary backup device. I could just see the cell voltage of Karpens Pile
be 1.00V but where the current has dropped to zero and is unable to activate it's
depolarization device any longer, And yet the curator is pulling it out and saying;
"Here it is gentlemen; Karpens Pile." There is another picture of those cells in
a box covered with Sulfuric acid corrosion. If they couldn't handle this correctly
then maybe they *should have* given it to the French. I suspect that they may
not have valued these much at first, but then history set in.
What I'm saying is eventually your cells may be the only working Karpens cells in
existence, so proceed with care.
:S:MarkSCoffman
Yep that's the one that did not recover. I will need to look into it further. Now I can't figure out how I'm getting 900mv. All the journals I've read have a much lower value . for example Google 13(2)_P77-101.PDF.
Aha my mistake.I thought silver vs secret meant silver with secret.ok no graphite lets go of H atoms very slowly.its not so easy to find exact numbers in lists pomodoro.you must remember we are working with galvanic overpotentials for batteries not electrolysis overpotentials.activation overpotential is the key,very dependant on material makeup,surface area,gas exchange rate etc.a number of factors.
Thanks marcscoffman.scientist viewers will accept it quickly but yes for the layman viewer a sealed system is best for conviction.karpens romanian device has air trapped in it so if there's a tiny hole in there it won't matter too much.sulfuric acid doesn't crystallize or dry out in open air either it stays in solution which is why I think he could say with confidance that that robust thing will last a lifetime and beyond.
I think we should seal gadget when we get the cathode sorted for max power what do you think pomodoro?
I just had an idea for a non-nanotech battery.
Sorry, I don't immediately visualize these ion systems / leakage systems.
Use semiconductor silicon slabs cut from a boule as the base metal for a battery.
Could use either acidic or basic electrolyte.
a) deposit anode and cathode material as slightly overlaping stripes all the way across
the silicon slabs. This will form the series cell voltage area.
b) manufacturer can form a silicon dioxide layer = glass insulator and electrolyte rejection.
(Semiconductor industry uses Fluoric acid to etch silicon dioxide off.)
c) manufacturer could also "radiate-inject" dopant metal ions into the silicon slab to turn areas
into N and P diode regions if you need to bias the base metal silicon on or off, if that will protect
it from corrossion. (You could artificially bias it with a voltage doubler if more is required.)
d) attach to a radial support structure as shown in the original Karpens Cell.
e) shove the above structure into a glass tube add electrolyte and seal.
....One may be able to do a glass-mat battery with above, glass proof of product
them move to available poly- plastic containers. If one needs to do depolarization
electronics for cell one could use use modified "lithium battery" like top compartments.
Interested in plating cost per square area, power per 1/2 square area.
Cautions about 2Lot thermal energy generators apply.
:S:MarkSCoffman
Thank you mscoffman.
Here is an update, this morning I found the silver electrode behaving sluggishly. It was not recovering to the 800mv mark in the 60 seconds any more, but more around the 600 mark, and the discharge was reading a lot lower, about 400uA. The electrolyte had floating bits and was darker. Even bubbling hydrogen had little effect.
The Pt/Pd still behaved well so it is the silver that is playing up.
I cleaned up the cell with fresh KOH, cathodized the Pd/Pt and anodized/cathodized the silver but still results are not the best. It looks like the silver needs to be cleaned up in nitric acid for it to work well again... While we ponder on this problem I set up the cell with the graphite electrode instead, anodized and cathodized as before. Now it works well, check out the constant 400uA and 40mV across the 100 ohm +15 of the meter, no need to pulse discharge this one!. Whats going on, surely the graphite must have a metal oxide contamination on the surface, but then again, the hydrogen gas in the solution should reduce it ? Check the link..
http://youtu.be/ezOAP8Ady78
Quote from: pomodoro on July 18, 2014, 12:52:13 AM
Thank you mscoffman.
Here is an update, this morning I found the silver electrode behaving sluggishly. It was not recovering to the 800mv mark in the 60 seconds any more, but more around the 600 mark, and the discharge was reading a lot lower, about 400uA. The electrolyte had floating bits and was darker. Even bubbling hydrogen had little effect.
The Pt/Pd still behaved well so it is the silver that is playing up.
I cleaned up the cell with fresh KOH, cathodized the Pd/Pt and anodized/cathodized the silver but still results are not the best. It looks like the silver needs to be cleaned up in nitric acid for it to work well again... While we ponder on this problem I set up the cell with the graphite electrode instead, anodized and cathodized as before. Now it works well, check out the constant 400uA and 40mV across the 100 ohm +15 of the meter, no need to pulse discharge this one!. Whats going on, surely the graphite must have a metal oxide contamination on the surface, but then again, the hydrogen gas in the solution should reduce it ? Check the link..
http://youtu.be/ezOAP8Ady78
The graphite behavior is interesting. Is it possible to leave it running for an extended period of time to see if it is decaying albeit slowly?
The graphite anomaly has been solved. I wonder if anyone here can solve it too, it has to do with the apparatus I set up not being perfect. its actually a big problem when studying this hydrogen powered karpen, especially because the hydrogen on the Pd/Pt will reduce anything it can over at the cathode electrode, and it means I have to run the silver again. :-[
Quite a few possibilities here pomodoro.you said electrolyte was darkish,means palladium particles expanded and dislodged or silver particles dislodged.electroplating must be tight-tight. It could also mean air was creeping in from a leak and discharged the cell.
You must shortcircuit these type cells for at least an hour after construction before taking an properly equilibriated measurement.
Quote from: pomodoro on July 18, 2014, 03:54:47 AM
The graphite anomaly has been solved. I wonder if anyone here can solve it too, it has to do with the apparatus I set up not being perfect. its actually a big problem when studying this hydrogen powered karpen, especially because the hydrogen on the Pd/Pt will reduce anything it can over at the cathode electrode, and it means I have to run the silver again. :-[
When you went to the graphite did you start with a fresh batch of KOH?
Use the PLATINIZED foil from your conductivity cell and see what happens.this will be a stable anode manufactured by factory.
Is your graphite dewaxed??
Are you in south africa,I'l come over and help.
Is that pure hydrogen.traces of H2S will fuck things up.
Pomodoro,please bubble that H2 through AgNO3 soln quick and tell me if it goes pitchblack.
The gas bubbler is a little too long and touches the bottom of the flask, hence the fit around the neck is not quite tight. I assumed that since the flow of hydrogen was quite high for the graphite, that no way anything would sneak in, after all when nitrogen is used nothing does. But the tiniest amount of oxygen does sneak in, hence the continuous current. Even the smallest trace gives a current! This is not all that obvious with silver but graphite loves to attract oxygen somehow.
The overnight silver problem may not be the same because I used a different attachment that just passed hydrogen on top of the solution. Flow was low but I'm not sure if O2 could have snuck in. The silver didn't look like it had any of the dark sulfide coating. Most of the floaters were white in color.
And the hydrogen is not UHP but industrial. It was going to cost me too much for the UHP. So it might have traces of oxygen. Even the UHP can sometimes have impurities as I found out years ago.
So the next cell will need to be different. Much,,much smaller, with hydrogen generated by electrolysis in situ, the oxygen generated elsewhere, and high vacuum silicone grease with ground glass joints used. No permanent melted glass for now as I need to take it apart for further tests.
I dont consider the week a waste, but it shows how many amateur scientists can screw up very, very easily, especially when just a trace of a substance can have a massive impact.
Industrial grade.probably H2S in there.even rubber in contact with electrolyte will leak enough H2S for poisoning especially stoppers.remove the reference electrode I don't trust it either.I've seen Ag2S precipitate from rubber stoppers before.
Use NaOH solution and Al for pure H2.or electrolysis.never ever use H2 generated from H2SO4 or sulphates,some reduction to H2S takes place.
If there's no H2S in that bottled H2 then its fine we can use it.just chek for H2S pomodoro.save the hassle of having to setup own H2 generator.
Bubble through Pb(NO3)2 solution aswell to check for H2S.no lead will precipitate.
I'll do those h2s checks and see what I can invent with some glassware. Profit is, what metals aside from Pt can I fuse with glass?
If you can rule out H2S in our H2 supply it boils down to 1)O2 contamination at the cathode.2)improperly cohesioned palladium.3)insufficient surace area on silver.just these 3
Fuse Ag,gold,or Cu wire through glass pomodoro
Pt wire will leak H2 through glass very slowly.its ok if we are doing temporary tests.
Fuse bare wires not laminated ne.laminations peel.electrolyte creeps.clean all wires in dil HNO3 before fusing.no dirt,preferably rough etched where fuse joint is to avoid pulling wire loose later
Which country are you in pomodoro cmon tell me (-:
I think I found problem pomodoro.the reference electrode salt bridge electrolyte was contaminating our electrolyte with Cl- ion.Cl- ion poisoning our cathode.abandon all reference electrodes in the setup from now on.they are not needed.
How much chloride ion can leak through this salt bridge in the middle of this ref electrode.that is the question.
The junction has KNO3. In any case the main problem is oxygen. There is a video which I have not uploaded as yet that shows the Ag karpen charge up to 900mv as soon as the hydrogen bubbler is removed and air allowed entrance .
The next karpen will be smaller, kept shorted ,sealed with visual means of observing a positive pressure inside it from the hydrogen.
Ok.If we can just get the same V that the chinese got with Pt/Au(not Pd in their study paper) 0.45v and at least one mA/cm2 and permanent.. Then we can pop the shampaigne corks.you now see how difficult it is just to contain H2 without a leak.you also now see how impossible it is if one doesn't know ones electrochemistry quite thoroughly.experience and knowledge are necessary.
Reference KNO3 wouldve also caused probs,its an oxidizer.
a U-bulb like this with borosilicate is easy if you have a lab.you can cntrol how much H2 you want sealed by size of bulb at the anode.the cathode side is last to be sealed with gas burner.this can be done very easy with plastic instead of glass.
So still use 1m koh , and the electrode, is it platinized and the other smooth gold? Did they use aluminum to generate hydrogen in situ?
They designed their test for only v-reading.their v didn't change one iota after 10months and they did short it inbetween to try annihilate it.they used smooth gold yes but we must use rough silver because we want power aswell as v.
No they didn't say how they generated H2.they just said it was pure.I assume they had it bottled in the lab.industrial grade is no problem as long as there's no H2S in there.
I'll give it a go, but Chinese scientific research is not too good right now, I can't possibly imagine how it would have been in the 80s!!
Don't underestimate chinese research pomodoro,they have a coupla trillion dollars loose change lying around,even then.ok so its going to be a factory platinized Pt/Ag rough in KOH sealed ok? Let's do it.remember,the goal is to make history here.our names will bring riches later.
Before I start fusing glass to metal, I'd like to try using good grade epoxy, no less than 1cm thick to seal electrode wires within drilled glass stoppers.Hydrogen will be tested with pb nitrate and a slight positive pressure kept within the cell. No continuous flow this time.
Okdoke.use copper,gold,silver wire through the seal just enough to get through to inside and twist tight onto direct leads.I'm estimating 0.4-0.6v overpotential dif.try not to allow capture of air before sealing or vaccuum will form and puncture gadget2
Heres an oxygen based karpen cell test utilizing two different fuel cell oxygen catalysts,silver and MnO2.note the power relative to the size of the cathode MnO2 crystal (1mm by 2mm cubed)30-40microamp.both surfaces have been treated for surface area.electrolyte is 1M NaOH.voltage is 0.1v at top discharge curves(actualy one interrupted curve shown).contact wires made of nichrome(contributes less than 0.5microamp)
I've nearly finished the electrodes, will post a picture tomorrow. How did figure an emf difference of 400 mv? You have the same conc of protons and partial pressure as the Pt electrode.
If gold gives 0.45 then Ag will give around the same pomodoro.its just power that we need to get from it.
I was looking at the silver vs secret chart oscilloscope reading and something doesn't figure.if air contamination was a real menace then surely it wouldntve flattened out like that.we need to do the manhatten test again because it takes at least 5hrs rest to regain equilibrium after a 12hr(overnight) shortcircuit.I think we was too quik to dismiss the manhatten test we shouldve waited,the current and voltage wouldve climbed further up had we let it sufficient rest.
Check out latest video on YouTube. Shows the effect that oxygen has on the cell. In the video I stopped h2 flow. The voltage immediately rises. I also quickly lift up the silver electrode and the cell instantly charges.
https://www.youtube.com/watch?feature=player_embedded&v=kBHBr_NNLS4
OK gents I present you gadget #2. A palladized etched platinum electrode fused to glass , a pure silver wire electrode sealed with electrical grade epoxy. Both electrodes have ground glass joints and are sealed against tubular cell with high vacuum silicone grease.
Cell with 1m koh is purged with hydrogen, silver is made positive for a few secs to form an oxide layer and cell is shorted out overnight.
Keep watching...
What's that bubble floating in the middle of gadget2 pomodoro? After you short the system for hours give the system rest for hours before measurements.it takes time for resaturation of sponge with H2 gas after being totaly emptied.it takes time for gas to diffuse through electrolyte.
That was just a preliminary test. No bubbles at all now. Currently discharging, just a few uA.
So the the h2 was burned up by Ag2O in this preliminary correct pomodoro?this just to prepare cathode right?
Correct. This test is for a few days only. To see how it compares to the other cell. Later cell will be used to test out other cathodes.
It is discharging at the moment. Earlier today, after a few hours of discharging ,I allowed it to charge up. After a few hours it never went higher than 395mV and hovered around the 391-395 mark. Tomrrow I will allow it to charge up again. Anything near 900mV will mean that oxygen has crept in again.
Going up as high as 1.1v doesn't necessarily mean air is getting in pomodoro I've done this hundreds of times with nickel/Ag/NaOH.if the anode is totaly saturated with H2 and the whole thing sealed off properly voltage can climb pretty high.I used to discharge overnight,rest the whole afternoon,measure in the evening,discharge overnight,rest whole day,measure in evening.you must give the thing ample rest after long run discharges in order to auto-resaturate.
You must make sure that you have a visible large hydrogen bubble in the gadget2 test so that we can see if it shrinks in size over time.that will mean air is creeping in.
Quote from: profitis on July 24, 2014, 08:26:57 AM
Going up as high as 1.1v doesn't necessarily mean air is getting in pomodoro I've done this hundreds of times with nickel/Ag/NaOH.if the anode is totaly saturated with H2 and the whole thing sealed off properly voltage can climb pretty high.I used to discharge overnight,rest the whole afternoon,measure in the evening,discharge overnight,rest whole day,measure in evening.you must give the thing ample rest after long run discharges in order to auto-resaturate.
1.1 v is for nickel though. This is different animal. I'm positive that the pd electrode surface and H2 will reduce any oxygen given time, but if it was up to the cell to do simply by discharge, it could take a very long time. A mg of stray O2 requires 12 coulombs to reduce. At a typical 12 uA, diffusion limited current that's a million seconds.
No pomodoro.a nickel electrode and a silver electrode in KOH under air will discharge all way down to,wait for it,0.1 volt,20micro-amps/cm2(bursts!) and stay there lol.so you know that if it stays up at 0.6-1 volt after repeated dischrge cycles it is definitely hydrogen giving that potential.nickel and silver under air infact makes a weak O2 karpen cell lol.once that Ni(OH)2 layer forms it goes totaly inert.
A mg of O2 contamination is one hell of a volume of air(a few mls?).if we can cut out contamination to a few micrograms/minute then air will reduce at a faster rate than it can be supplied and cut its voltage contribution to negligible.its a very difficult task getting H2 contained without a leak which is why I was all for the flow-through method of gadget1.if we can repeat gadget1 but carefully making sure no leaks then it would be a good reading.the outlet pipe should be dunked in a beaker water so outlet H2 can bubble out without possibility of significant air backwashing in.
I would think that a small positive pressure should be enough to prevent intrusion and / or make up for H2 leakage. I don't think you need to have a measurable continuous flow to overcome glass / metal seal leaks.
Your palladium electrode and silver electrode once totaly discharged under pure air should come down to roughly 0.1v and a few tens of microamps/cm2 in other words another O2 karpen.
True @mark E.but you'd need to see that the pressure is maintained in order to know that pressure is maintained.a valve on the gadget1 gas exhaust pipe is one way to do this.
Pomodoro,you don't even have to short a sealed device to rid it of O2 traces.self-discharge of H2+O2 happens at surfaces of both catalysts spontaneously and completely within 2days.the problem is it causes massive vaccuum if too much air was in there,then that punctures a leak in the device.
Quote from: profitis on July 24, 2014, 12:00:57 PM
True @mark E.but you'd need to see that the pressure is maintained in order to know that pressure is maintained.a valve on the gadget1 gas exhaust pipe is one way to do this.
Or a pressure sensor should do. A small fraction of a PSI over ambient should cover things. There are lots of very nice analog and digital pressure sensors around that cover gauge pressures well below 1 PSI. A simple voltage limit alarm can be devised easily enough to trip and hold an alarm if the gauge pressure gets too low.
Overnight experiment did not give positive results. After shorting out all night, the cell voltage sluggishly crawled to 192 mv after one hour and stayed there. Discharge was weak. So another gadget has been constructed. This is similar to gadget 1 but has a lower volume and can be evacuated. Currently it has been evacuated till the water boiled, filled with hydrogen with a slight pressure and is now shorted out.
Or he could just lead the exhaust pipe under beaker water of a fixed level and slowly bubble out,one at a time..
Pomodoro,how much H2 was visible in the overnight test.
There was none as I did not leave any gas space.
.mustve burned.I'm also beginning to think that direct exposure of the palladium to H2 is important for rapid voltage climb.certainly from perspective of rate-limited diffusion but we'l see with this new test.
Got the graphite going over the weekend. Check out the current, 400 uA for 10 mins , is it really oxygen seeping in? It is dropping slowly .Kicks butt compared to the silver. Let's see what it looks like in 2 days.
The graphite setup is highly likely to fail for two reasons:1) air will undoubtedly creep straight through pores if it is a dewaxed rod.2)air will likely creep through side pores if it is a waxed rod. Wax will also saponify with KOH and may or may not cause problems at the anode.all graphite rods have to be dewaxed on a hotplate,wholly immersed in container with lead wire attatched.only the wire may emerge.
Pomodoro,image number 20140724102633 is a discharging H2/Ag2O cell am I correct.look how limiting the diffusion of H2 gas through electrolyte is on a normal galvanic cell!! A few microamps, my god.
Sorry but after 5 minutes I still cant locate the file, but probably not Ag2O as the discharge is in the order of milliamps when its black.
The graphite is probably not waxed. Its smooth. If waxed the KOH wont saponify it as it would be parrafin wax. I did the graphite so as not to waste the second cell over the weekend. I'm thinking that the graphite, which is not smooth any more where its been used as an electode, has absorbed some air over time and is now reducing this absorbed oxygen. If I really wanted to test it I would have to snap a piece and wrap it around the silver electrode, then stick it in the cell, because I also agree that the current setup is not too secure.
I'd love to test copper soon because I can fuse that in glass. Still lots to learn at the moment, but in a few months some real truth will come out of this.
I'm talking about your photo on page 17 pomodoro.what's going on in this pic,what is that bubble in the middle composed of. All graphite is waxed all the way through as binder and causes 2 problems: the fatty acid content definitely saponifies with KOH to some degree.the wax also drasticly reduces clean electrode surface area.alkaline zinc batteries use stainless steel rods instead of graphite nowadays.all graphite must be dewaxed then wholly contained in the system,there must be absolutely no possibility of air leaks.I've done tons of tests with carbon and it works beautiful in these cells except it takes much longer than silver to let go of atomic hydrogen.about 3 times longer.
Copper..mmm (-: I don't want to let go of too many secrets here but yes it will be nice to try it.
The only batteries that you will find with exposed-to-air graphite cathodes are zinc-air or indeed H2/air fuel cells
That pic was after discharging the oxide. It always remains brown but the pic made it look black. The shorted current was very low, but the yellow clip was not in the correct place and when I moved the cell air came in and the volts went up. So I refilled the cell with koh and saturated with hydrogen but left no bubble to make sure no air snuck in
Are you sure that when you moved the clip that it didn't just make better electrical contact? Happens a lot,with everybody.I'm worried when you say brown because Ag2O is pitchblack and reduced Ag20 is grey-black.I hope no sulfur compounds are in that epoxy because it will cause a browny-black colour if H2S gets in.the Ag2S layer tends to drift off the cathode and darken the whole solution if this happens.in future we must throw a small shiny piece silver into the bottom of container just to check if it goes black.if it goes black then we have to avoid wetting epoxy.I still think a gadget1 type device is best option pomodoro
That pic that I posted of me holding up a piece jewellery silver was brownish due to being left exposed to atmosphere for months.it got a coat of Ag2S.
You must always have excess visible H2 gas in these systems that you can see with the naked eye otherwise you can never know if you've sprung a leak or have limited re-uptake of H2 due to hampered diffusion or depressurized the cell from H2+O2 recombination.
Here's the advantages of a properly sealed and exhaust-piped gadget1: 1) adequate exposure of anode to H2 eliminates rate-diffusion problem.2) any tiny O2 contamination will not depressurize and puncture cell and is quikly diluted.3)electrodes can be easily replaced or disassembled and modified to get desired result.4)electrolyte is far away from interwire joints and rubber stoppers.5) H2 flow can be increased/decreased at will.6) everything in the cell is clearly visible.
I still prefer type 3, but with some pressure sensor simply because constant bubbling introduces other contaminants from the bottle. When I ran gas chromatography labs we needed oxygen traps on the uhp hydrogen because it still contained traces of oxygen and wrecked columns after months of usage. When I dismantle this gadget 3 I will place a hose on the tap with the open end under water to check for a vacuum or positive pressure. Another run can have the pressure regulator apply a small positive pressure throughout the run. Regarding the treated silver, it is definitely a brown color, not grey.
Here is my email, if anyone prefers, so we don't clutter the forum with too much of the preliminaries and keep the Russians a step behind!
SirXPomodoro@gmail.com
Remove the X first!
I doubt thers more than a few parts/million O2 in that H2 canister pomodoro.the factory that made it wouldve been forced by regulations to make sure of that.it will almost instantly recombine on contact with our catalysts its not a worry,leaks are enemy number 1.H2 is a highly agile molecule.
How did the latest test go pomodoro,give it rest for a few hours before reaching conclusions if it was shorted overnight.your lab has got all the necessesary ingredients and equipment for successful tests,we must be scientificly efficient and use it wise while we can.
The brown color on that silver is worrying,is it pure silver straight through?
No idea, I'm home for the weekend. Remember I'm using industrial grade hydrogen for now.
Any grade H2 canister will be forced by regulations.is that pure or plated silver?where did you get it?
It is silver wire for chemical experiments, but have no idea of purity. I did not buy it myself.
We can test it by dissloving a small piece in HNO3 when it comes out of that test.there must b no color change.we are getting closer to our set goal,to measure stable power outage from an gaseous overpotential difference.when we do this in the milliamp range,we make history.
I just want to point out that your cathode has only about 1cm epoxy between itself and air pomodoro.air will get in all the way through that wire bundle under the jacket.this is why I always use a single strand bare wire for contacts.I have to be cracksharp with my observation here otherwise scientist critics with sarkeizen-type characters will bash us at the first weakpoint they see (-:
Quote from: pomodoro on July 25, 2014, 08:54:15 PM
I still prefer type 3, but with some pressure sensor simply because constant bubbling introduces other contaminants from the bottle. When I ran gas chromatography labs we needed oxygen traps on the uhp hydrogen because it still contained traces of oxygen and wrecked columns after months of usage. When I dismantle this gadget 3 I will place a hose on the tap with the open end under water to check for a vacuum or positive pressure. Another run can have the pressure regulator apply a small positive pressure throughout the run. Regarding the treated silver, it is definitely a brown color, not grey.
I think that the small positive pressure is the way to go.
Quote from: profitis on July 26, 2014, 06:00:30 AM
I just want to point out that your cathode has only about 1cm epoxy between itself and air pomodoro.air will get in all the way through that wire bundle under the jacket.this is why I always use a single strand bare wire for contacts.I have to be cracksharp with my observation here otherwise scientist critics with sarkeizen-type characters will bash us at the first weakpoint they see (-:
Make any comments guys, I will try my best. These cells are designed to test the principle for a few days at a time. With positive pressure surely any tiny leaks such as the those should be covered right? When I get back we will see if #3 worked. If not next step is to test the silver and to pressurize the flask. The only reason I did not do it permanently with a regulator on the bottle is that the quick fit tap pops off as it can't fit a clip like the yellow ones in the picture. The clip has no neck on the tap connector to press down on. That's why in the pic you see a clamp just above the tap. It is pressing down with force.
I agree that the positive pressure should take care of small leaks and prevent infiltration. I say proceed with the experiments and let's see what they show.
Positive pressure is good but we have to be able to monitor it on a guage to make sure its there.if the supply tank has a guage meter exellent.a gadget 1 device can be designed for purging plus static pressure by blocking or tapping exhaust.we would have to be careful that the pressure doesn't puncture a hole through weakest points though.
Check out these oneway valves.one of these on the exhaust pipe and under certain level of water would ensure pressure everytime the device is purged.
Pomodoro,for the next test please make sure that the palladium is just touching the surface of electrolyte with one corner of that foil,capillary action will do the rest.
Try not to bend,touch black foils when assembling,this dislodges coating
Ok, the weekend experiments were no good. The gadget #3 only recovered to 40mv. I shook the flask and it rose to 350. Shorted and got over 1mA peak. And left it alone. It only rose to 95mV in an hour. On inspection it no longer had any positive pressure, but a very slight vacuum.
The graphite as expected lost all power.
So now #3 is back with some improvements as you can see in video.
1.Electrolyte is lower in volume, allowing Pd into gas phase.
2.Purging of electrolyte went on for 10 minutes - Voltage dropped from 900mV to around 500
3.Tygon tubing used all round
4.Exhausted hydrogen passes through water trap
5. After 10 minutes trap is sealed off, allowing a small pressure buildup of hydrogen from cylinder regulator. A tiny leak is allowed to purge a very small amount of hydrogen through system
If this don't work I don't know what will!!
Pomodoro you are going above and beyond in your efforts. Hopefully, this latest appraoch will yield interesting data.
Cheers markE!
Very early days, but for the last few hours it is constantly supplying 20uA at 117mV, stable, through the 50 uA galvanometer.
Lets see how looks toorrow.
If its stable tomorrow we have something to work with.
Yes this is the best way to do it pomodoro.hydrogen is a bitch! If it remains stable at 20micros I can assure you it will leap up near or past the one milliamp area when well rested.0.5v sounds about right(remember the chinese 0.45v).did you test a piece silver pomodoro?
The rate of exhaust looks perfect in that video.
I see not much of cathode surface area is exposed to electrolyte but if it stays at 20micros at bottom of discharge curve its quite a power there.
Please put all preliminary vids here before on youtube so that I can immediately observe pomodoro.there's no desktops in this household there's never been a need for one.my phone can't open certain youtubes for some reason.
Mr profitis what do you predict would happen if the silver is replaced with Cu or Ni?
I can give no details on copper over here mr pomodoro but you may try it if you wish (-:. It is a member of the silver family and gold will do extremely nicely as cathode.nickel will do nice with our silver and I think that should be our next bash? what is the latest reading on gadget3 mr pomodoro?
Next reading 12 hours away!
Need to find best cathode material then make cell with huge cathode and small volume. Also see if cathode is activation or diffusion limited. Finally make a sealed cell.
Ok pomodoro.one thing I have actually learned from this series of tests is that diffusion rates definitely affect voltage and current quite large(I've always worked with minusule samples here)I think we should try a massive silver and graphite cathode and try variations of electrosurface prep methods on both electrodes.
OK cell was still working. 95mV through galvanometer @ 16uA. Solution was cloudy white. Now trying original silver electrode overnight.
Why was solution cloudy pomodoro?
Not sure. Frit getting corroded by NaOH? Let's see tomorrow.
Is this the same cloudy that you saw in the manhatten test? Can you send a closeup pic of it.
Try not to get the epoxy wet.did you chek for sulfides in that H2
Electrolyte should remain perfectly clear permanently with Pd/Ag/KOH/H2
See
Could be colloidal sulfur from reduction of sulphates in electrolyte.could be white phosphorus from phosine in H2.could be AgCl floating off cathode from Cl- in electrolyte.is that cathode still brown-black.is that KOH lab grade,did you put reference electrode in there pomodoro
I've used caustic soda from supermarket in all my tests with no probs.perfectly clear.
Could be overnight sabotage lol.who was in the lab lastnite
Was the exhaust water also milky pomodoro.this will give us a clue
H2 passes lead nitrate test. A.r. grade koh. Milliq water.
The exhaust water pomodoro???it was milky??
No, nice and clear.
Tried out 1m sulfuric as well, not as good as OH.
Could be ammonium carbonate or urea from traces 2NH3 + CO2 +H2O > (NH4)2CO3 floating around salted out by KOH.so what test is being done now pomodoro??
The problem once we have a permanently sealed gadget will be the alkali etching glass. Glass won't last 50 years with 1M hydroxide.
That's the least of worries mr pomodoro,there's plenty types glass,plastics,ceramics nowdays(what do they make NiMh batteries with?).our only worry is to show a stable overpotential diff over a period of about a week.a fuel cell without air is all we need to make to nail it down.
We should record the days ambient temp aswell to get an idea of performance.perhaps the sample dropped to 16uA today and will rise to 2OuA tomor then 18uA the next.I'm already confidant with the latest data,it seems to have equilibriated.
I was thinking that the "eternal" part of Karpenns cell is perhaps being mis-considered
here. Only the original Karpenns Cells needed to be "eternal" because that was a signal
flag, as it were, that there was a super chemical energy potential reaction going on.
This was because almost no-matter how low the energy drain of the depolarizing
load device was, eventually it would require more than the total chemical potential energy
originally in the cell when it was started long years ago, to have been operational for as
long as it was.
So the progeny of Karpenns Cell should have to exceed only the calculated
quantative analytical total amount of chemical energy available at the start
because that can reasonably be estimated, for it to be operationally useful
in tapping into the 2lot thermal energy to support its operating cost. There
are actual reasons *against* mass producing "eternal" functioning systems
having to do with electronic systems continuing to run after they have
exceeded their useful lives and having been scrapped.
For reasons listed below I feel that 2lot violations may be only a side effect of the
system operation and that atomic transmutations will eventually leave the chemical
system contaminated, anyway, after a very long period of time.
It is a fact of science; "That hydrogen atoms compressed to 200 atmospheres and placed
in a metal tank - thermal neutrons come out of it. It's been calculated that PEP-II
neutrinoes have the exact energy required to do this operation Think of what the formation
of a electrically neutral particle from a protium ion and an electron looks like from the
standpoint of the chemistry of the tank. This is not an operation common in normal
chemistry.
:S:MarkSCoffman
There is even no need for calculations @markscoffman.who ever heard of a battery that maintains its full voltage and wattage after 60years?even without discharge? Its unheard of to have any battery that has absolute zero self-discharge.a 1000year shelf-life.all batteries self-discharge over the years and drop in wattage and voltage on just standing and doing nothing!
Your reasons against mass production may very well be true but thers ways to manufacture to ensure limited lifespans.
Found cell very weak, frothy electrolyte and the silver electrode had the gray deposit easily wiped off. For now going to try copper with stirring and no bubbling of hydrogen.
Copper cell being shorted is allowed to recherge and discharged through 6kohm galvanometer
Focus on the Pd/Ag Ni/Ag pomodoro,success is certain with those 2.its just a matter of playing around til u get it right.we must try get back to 16uA constant bottom of discharge.that is already indicative of total success.reanodize-cathodize the Ag in Na2CO3 for more surface area.your experiment with copper is expected to be weak power.
I need stability for a start. Silver is losing power for whatever reason. If Cu is stable I can tinker with it and tackle Ag again. I tried carbonate treatment. Worked very well initially but again failed overnight.
All of these cells should theoreticaly lose power all way down to a few micros on constant short-circuit discharge.its the accumulative wattage at the top of a well rested cell curve that matters most from a practical pov.I see your palladium is a bit too much underneath electrolyte in this experiment but at least some is exposed.I see you didn't blacken your copper either but ok this just to chek 4 stability.
You might want 2 try blacken silver in HCl aq but you must cathodize hectic and rinse dam fast(hot water) to avoid re-oxidation in air exposure.its possible that the black layers were loose and actually insulating our silver from electrolyte,most of my success came from grey spongey adherent coats.your prior method of discharge of a h2/ag2o cell seems best way to get adherent coat
Chek if you get a precipitation with KOH vs NaOH I've got a feeling of bicarbonates forming(CO2 impurity frm your H2 ) which will salt out of concentrated base.just bubble ur gas straight thru respective bases in a beaker.chek if the mystery nuisance precipitate dissolves in excess h2o this will give massive clue
Copper test was a success. Nothing changed overnight. Electrolyte still clear, 1ma meter gets slam dunked after recovery.
Nickel plated copper but got much smaller voltage and weak current. Its too similar in characteristics to Pd with H2. Stripped off Ni and plated pure Ag. So far a bit better than Cu but not greatly at equilibrium but has more punch when discharged. Perhaps other silver electrodes were impure, hence the ppt. I know plated metal is not going to last but using it for short term tests.
Exellent pomodoro.I think its our surface prep of silver that's messing us around.etch that silver in HNO3,rinse,then shove it into next test(don't anodize-cathodize)it will be stable.main priority now is just stability.keep the copper experiment going meantime let's see what happens..
Don't jump anymore between experiments when we have stability.let's put the test of time now..
Use 925 jewellry silver for the longrun tests pomodoro.it will not fail us.
Mystery pecipitate couldve been unreduced Ag2CO3(yellowish-white) still embedded in the black layer that spread over entire solution.that has happened to me before.what happens is the Ag2CO3 dislodges from silver during prep then withstands electroreduction.that's why you have to cathodize it shitless to get back to Ag if twas thick coat.An black Ag layer that is too thick and fine will also naturaly trap too much H2 buildup in its pores and insulate from the gadget electrolyte and hamper gaseous diffusion away from the cathode
To test for purity of silver,simply throw into HNO3,it must give clear solution and brisk evolution of NO2.jewellry silver will give a blue tint due to trace copper.AgNO3 solution will evaporate and decompose direct to silver-color silver when heated on burner in a testube(300celcius)
Cheers for all the advice. I will test purity soon. I can dissolve in nitric and test ppm of silver with icp. Time is my enemy at the moment. There are a few more metals of like to try as cathodes and I will then run it for a week. When I anodized the larger silver electrode, some light blue carbonate formed. You are spot on about the reduction being difficult. With the copper no conducting oxide formed in koh it kept flaking off as it was being produced. So a simple nitric etch was all I used.
I'm glad we got that problem out the way pomodoro a sigh of relief coming out me now.you might want to try graphite now aswell,fully dewaxed on hotplate,and inside not outside the device.success is imminent.
carbon-carbon battery
https://www.youtube.com/watch?v=D6D0lKPY_as (https://www.youtube.com/watch?v=D6D0lKPY_as)
https://www.youtube.com/watch?v=rMzI9WDaAvU
If murray is using paper inbetween electrodes its probably a fuel cell.cellulose undergoes hydrolysis in alkali and breaks down to sugars fuel.murray must repeat with glass fiber inbetween.
Quick update. Pd/Pt vs Cu. Worked well after 3 days. Decided to try a cheaper version for building a higher voltage pile. Now trying Palladized Cu vs Cu. Also now using uhp hydrogen. I'd like to be able to power a device constantly, these cells discharge ultra quickly. Any ideas on microamper motors requiring a volt or so, or a pulsed milliamp motor that keeps spinning till the next discharge some 30 seconds later?
Quote from: d3x0r on August 03, 2014, 03:47:51 PM
carbon-carbon battery
https://www.youtube.com/watch?v=D6D0lKPY_as (https://www.youtube.com/watch?v=D6D0lKPY_as)
https://www.youtube.com/watch?v=rMzI9WDaAvU
Awesome, check out how he gets so excited by the discovery! He forgot to shout eureka out loud.
A galvanometer with an on-off alarm switch circuit is one way to display power continuously pomodoro.your going to have to play around with the device to figure how many seconds inbetween pulses is sufficient rest-time for stability.the electronics geniuses on this website should be also able to give ideas if we ask them about pulse motors.the diagram below is one way to make a sealed device with a oneway gas valve attatched.aluminum foil is tossed in before screwing valve onto the device and enough gas generated to purge all air and fill with slight pressure.it must be put underwater briefly when gas exits to make sure that gas escapes only through valve and not leaks.you have to play around with Al foil and caustic soda beforehand to get an idea of what volumes H2 is generated per unit foil.
A pendulum swinging an iron ball on a long thread near a switch-electromagnet just came to mind for demo.easy to adjust for timing.
Coat that palladium onto nickel foil for best results pomodoro.you may lose quite some power if you coat on copper family.
Coat Pd onto stainless steel shaving blades,another cheap option.make sure plating solution is acidified with ammonium chloride or dilute acids(acetic)
Tried the Pd/pt vs Ag with tetrasodium EDTA instead, to prevent the gradual loss of power, but deterioration of Ag surface Is visible - a gray film where immersed in electrolyte.. Same deal with conc. Ammonia. I'm surprised as I thought these would keep surface clean but leave elemental silver alone.
Nooo pomodoro.NH3 and most amine compounds viscously attack silver and take it into solution.this is why they are used to clean silver,they strip the surface clean.forms complex silver-amines which then probably reacted with cathode H2 and partially reduced to grey Ag.use only KOH or NaOH or Na2CO3 in the silver cells.use etched silver not anodized-cathodized like we was doing before.youl get silver plating direct onto your palladium anode eventualy within the gadget if you use ammonia as electrolyte
Quote from: pomodoro on August 04, 2014, 07:58:50 AM
Quick update. Pd/Pt vs Cu. Worked well after 3 days. Decided to try a cheaper version for building a higher voltage pile. Now trying Palladized Cu vs Cu. Also now using uhp hydrogen. I'd like to be able to power a device constantly, these cells discharge ultra quickly. Any ideas on microamper motors requiring a volt or so, or a pulsed milliamp motor that keeps spinning till the next discharge some 30 seconds later?
A synchronous P MOSFET switch into a capacitor would do the trick.
Thanks marke will look into that soon.
Profitis any chance that the power from this device is the double layer charging to the Ag reduction potential and discharging when connected to the lower voltage of the Pd hydrogen/ proton couple?
No pomodoro.there's definitely h2 coming out the cathode(you can't see it,bubbles are too small and diffuse rapidly away)all passage of faradaic charge must be accompanied by redox reaction otherwise electroneutrality is violated.its just catalyst spillover from textooks.
For you pomodoro http://www.nature.com/nmat/journal/v12/n6/abs/nmat3620.html
Lol @sarkeizen..ever tried to seal hydrogen gas in a leakproof bulb with 2 wires sticking out of it? I thought not
What's the status pomodoro?? So we have stablility for Pd/Cu,Pd/C,Pd/Ag correct??
Relax @sarkeizen it won't be long now.what you can do in the meantime is quickly build my other design under the threadname 'perpetual batteries by vasilescu karpen' for a direct violation of the second law thermodynamics.
Cheers for link, I'll have good read of it later on today.
The stage I'm at is testing the pure Silver foil instead of the wire or plated copper.
Need to make sure the system is steady for a few weeks before I make the permanent totally sealed in glass version.
Well things are not going too well. A nice polished and solven t washed silver cathode in 0.1m na carbonate does very well initially but after discharging for 2 hours recovers very slowly and each time the voltage is always weaker. Silver is still nice and bright. Intake the electrode out for a second and when I put it back all is good again, for a while. I'm starting to think that the cathodes that worked had slow to react oxides from the anodizing process which can power the device for a long period of time. :-\
0.1m sodium carbonate is too weak.its pH is much weaker than the KOH so anode voltage dived and cathode voltage rose.you must use concentrated Na2CO3 if you do use it. Its possible that you did leave some oxides of silver in samples but its also possible that hydrogen buildup was too much in the layers that were too black and fine.you have to anodize your Ag briefly,cathodize it shitless for thin grey-black adherent layers that won't cause H2 buildup blockage.
If you can get for the silver what you got for the copper for 3 days it is safe to seal pomodoro.all traces surface oxides wouldve been obliterated after about 1 hour shortcircuit.obliterated by the shortcircuit AND obliterated by direct exposure to H2.
Do not be impatient after longrun shortcircuiting.sometimes what happens is voltage climbs back up fast and current buildup lags behind slowly,then after a certain Pd/H2 saturation point current recharges fast.if you've discharged for a few hours,let it rest for a few hours.
Can you get hold of a chunk pyrolusite pomodoro.
Back to basics. 1m naoh fresh Pd/pt silver plated copper. Uhp h2. Shorted for the night. Let's see in the morning.
Ok pomodoro.meantime please try get hold of a piece solid pyrolusite,we can build a nice potent oxygen karpen for the viewers meantime
Don't think I have any pyro. Anyway I better concentrate just on this hydro karpen for now, before I throw in the towel from stress.
The current idea I have for a sealed version is to use a cleaned out fluorescent light tube. The glass to metal seals are already there, I just need to cut the tube close enough to the end so I can work on the electrodes . It wont be that easy but worth a shot.
Gonna keep this karpen going for a week if it behaves, if theres constant deterioration I wont bother with a sealed version.
Ok pomodoro.this type research involving hydrogen encapsulisation is really for the multimillion dollar funded labs with all the necessary containment equipment eg cold fusion labs or NiMH/fuel cell research labs but you can do the basics at least.focus entirely on the Pd/Ag,Pd/Cu systems now.if we can get any of those two stable in sodium hydroxide we make history here.
I also want to suggest long see-through polyethylene tubes that are easily shaped and sealed by melting shut over single-strand copper wires like in my straw-v-cell picture.you seal one side at a time and simply electrolyse for h2 encapsulization
I know for a fact that the H2 karpens can be permanently stabilized if done right,why? Because the O2 karpens are all permanently stable.
I have "invented" a depolarizer device as I suspect the energy source you are chasing shows
up in unconnected piezo-crystals as well. Over 24 hours a standard piezo crystal sounder will
charge up and can then be shorted to get a small pulse of free electricy. I was going to use 12
of these piezo sounders in a circle, then discharge each one sequentially every two hours to
power the microwatt motor of a mechanical digital wrist watch used as an inverse electrical
distributor. So this construct is in effect a perpetual motion clock.
There are two types of devices; one runs on it's own battery for the laboratory use. And the
other can be self powered from it's battery cell for if you want to try for Karpen's record. I'm
telling you this so you don't have to worry that such a device exists. If you need them rapidly,
one could put effort into building them. It takes advantage of the fact that a mechanical
wristwatch with a plastic face watch-crystal runs on microwatts of energy.
---
I favor building this depolarizer in two parts one that does the depolization and a display
"header" circuit which can do the user display. The header can consist of a capacitor, a resistor ,
a flashing LED, and a LCD wristwatch with no battery.
resistor = dummy load to indicates that the battery cell power has not decreased significantly over time
flashing LED = that the device is producing power right now
LCD wristwatch = if the wristwatch has not reset then power has never been lost.
Karpen's electromagnetic depolarizer doesn't do each one of these well and would be complicated and
expensive to manufacture today. Other another hand production cells should use the somewhat more
inefficient semiconductor approach.
---
I will leave my battery cell chracterizer machine idea for a future post.
---
This power pulse effect creates a very narrow PWM window, if that could be eliminated
it would result in significantly higher average cell power. Pomodoro should not
become so enamoured with the slam-dunk-effect so that he then misinterprets
the meter pointer "sticking up there" as a bad thing.
:S:MarkSCorffman
Nice @markscoffman.I've seen those piezospeakers self-charge and read a thread on here ages ago about somebody finding the best piezo that they could find giving quite a few micro-amps every few minutes.your idea of putting them in sequence is exactly what karpen himself did with his museam piece,two in sequence for his pulse motor.the thing about karpens is you can stretch their discharge curves wider simply by cramming more surface area into electrodes.they can infact begin to look like a normal battery's or supercapacitors discharge curve theoreticaly.the more surface area,the less time inbetween pulses would be required.
Well guys, its been fun, but I must now admit that I'm about to call it quits.
18 hrs ago, I made the same cell that worked very well about a week or more ago. It was discharging rapidly, recharging to about 800mV within a minute. I short circuited it for 18 hours. When I allowed it to recharge, it only reached 30mV in 3 hours.
The only difference is that this time I forked out for an ultra high purity hydrogen gas bottle. I was using industrial hydrogen before. I also used sodium hydroxide instead of potassium hydroxide, but this should have no bearing on the result.
My suspicion was that the reason why the other cell worked was that oxygen was getting reduced at the cathode. So to prove this, I removed the cathode out of the flask for 2 seconds, put it back, and abracadabra, the cell is once again working perfectly.
I'm giving this one final shot, with the graphite rod.
So to properly prepare it profitis do I dewax it by heating in in hot caustic soda soln, an then cathodize it for a few hours to remove any contaminants?
pomodoro thanks for all the work that you have put into testing the concept.
Quote
pomodoro thanks for all the work that you have put into testing the concept.
+1
Lol.remember when I thought pomodoro was markE or sarkeizen...just 3 days ago pomodoro was jumping around asking about pulse motors and how to build one,why was he doing this?
It looks like I will have to put up a demo myself
Quote from: d3x0r on August 08, 2014, 02:30:29 AM
+1
Thanks Guys, I enjoyed the research, although it cost me a few dollars too many. A few more tests to be done before I pack up, but I am totally convinced that complete removal of oxygen and any oxides from the cathode surface render these hydrogen karpens useless. Absolutely for certain for the silver cathode.
Electrochemically it makes sense, the voltage of the inert silver initially shows that of the oxygen-OH/Water couple. The kinetics of this is slow on silver and takes a long time to be fully discharged. Once all traces of oxygen have gone, the next dominant couple is hydrogen- protons/water, this voltage is that of the Pd/Pt , with some differences due to the slower kinetics on the silver, hence the low equilibrium voltage.
Exactly why the other metals I tried were not as good as silver I don't know, but perhaps the oxygen doesn't adsorb on their surface as well or the hydrogen/proton couple is more active on their surface, reducing the dominance of the oxygen/OH- couple.
In all cases, once the oxygen is gone, power is gone too. Any brown black coatings on the cathode should be avoided in tests as these could be slow reacting oxides that could power devices for weeks on end.
In direct contradiction to the research of chinese government laboratories @pomodoro.totaly stable Pt/Au,Pt(shiny)/Pt(black).
In direct contradiction to common sense too:all oxygen karpens eg. Ni/MnO2,Pt/Au,Ag/Ni,Ni/C,Pt/Pd,Ag/MnO2 etc totaly stable permanently
In direct contradiction to the textbooks too: silver hydrogen electrodes have a complete different voltage to platinum hydrogen electrodes according to your posted pdf on silver overpotentials
Not true, the rest potential of silver in alkaline solution in a hydrogen atmosphere was found to be only 4.6mv different to a pt in the same solution.
http://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/24795/1/13(2)_P77-101.pdf
Quote from: profitis on August 08, 2014, 04:08:30 AM
It looks like I will have to put up a demo myself
Attempting to back your own claims has always been a good idea.
Pomodoro,I'm going to ask if you can do us(all) one last favour.can you please measure the potential difference between palladium and the legendry MERCURY,king of overpotentials(O.8v +)under hydrogen gas in 1M caustic soda and report your result here for us.
I've already done that when I dipped the copper electrode in mercury and painted it till it was shiny with hg. It was not high. I have to look at the book at work and will also do it again on a video next week instead of doing graphite again. Then I'm packing up. Thing is profitis the hydrogen overpotential in books is what is required in electrolysis mode to generate hydrogen on that metal compared to a Pt in same solution. It doesn't predict the electrode rest potential one bit.
I'm disappointed the experiment failed for me but it shouldn't stop other keen discoverers doing their own tinkering.
Pomodoro thanks again for all the time and money you have put into testing out Profitis' ideas. I think that you have gone above and beyond with your efforts. Despite the negative results, well conducted experiments like yours are useful demonstrations of the care that it takes to conduct a good experiment.
If Profitis wishes to challenge your results, then I think he is going to have to come up with those text book references that he has long claimed back his contentions, and/or conduct defensible experiments such as you have, but which generate results consistent with rather than contradictory to his claims.
Thanks pomodoro.you want to literally try liquid mercury in a pool at bottom of flask,one strand thin mercurized(by dipping in Hg(NO3)2 aq.) copper wire in contact with it.mercury has such a high overpotential for H2 that even at current densities of less than 0.0001A its voltage is around 0.6-0.9 according to textbooks so it looks a highly promising candidate.graphiteis a must-try too for 2 reasons,it has also quite a monster overpotential at minute current densities and according to wikipedias list a very large ACTIVATION OVERPOTENTIAL.graphite is also infact more chemically inert than our metal counterparts.
I find it impossible for every single known inert material to register the same voltage as the standard hydrogen electrode,otherwise they wouldve used any material as opposed to platinum(black) for all standard reference measurements.many labs around the world have already measured the classic platinum black vs platinum shiny hydrogen rest potential and it is absolutely not the same,and that's both made of the same material(!)
The details of karpens hydrogen experiments seem to be very hard to track down on the net and I would appreciate it if anybody can locate those papers.piles a hydrogene empruntant leur energie au milieu ambiant.Acad de Sci,paris 1948 t.218 p.228. Also piles a oxygene empruntant leur energie au milieu ambiant.Acad de sci,paris 1944 t.226 p.1273
Quote from: MarkE on August 08, 2014, 10:14:05 PM
Pomodoro thanks again for all the time and money you have put into testing out Profitis' ideas. I think that you have gone above and beyond with your efforts. Despite the negative results, well conducted experiments like yours are useful demonstrations of the care that it takes to conduct a good experiment.
If Profitis wishes to challenge your results, then I think he is going to have to come up with those text book references that he has long claimed back his contentions, and/or conduct defensible experiments such as you have, but which generate results consistent with rather than contradictory to his claims.
Thanks for your kind words MarkE.
I've worked as a chemist for 24 years but I am not an expert electrochemist. Now let me admit that electrochemistry upto 3rd year university level is about where it stops for me. Any more , such as some of the heavy stuff in the paper I posted is above my level of understanding. It would take a person with a phD in electrochemistry to really understand every aspect of such research.
Although a scientist I do occasionally look an non conventional theories with an open mind. The Karpen pile popped up on some random google search and I took a liking to it, simply beacuse it involves electrochemistry and I was able to gather the required gear.
I understand that there are occasionally massive egos and other obstacles in this field, but I focussed on the task at hand, nothing more.
I seem to detect that in this Karpen field of study, on this site, there have possibly been heated discussions, but I have not at all bothered to search or read any other posts, except for this thread, so I still don't know what exactly Profitis or others has said and I dont feel like bothering to read.
So, as you have seen, there were some goofs, some great initial results and finally some not so great ones.
I however am completely satisfied with myself, that I learned from the initial mistakes and the last unsuccesful experiments were indeed correct.
In electrochemistry, dioxygen is a real problem. Any dihydrogen really needs to be passed over very hot copper turnings or powder before being introduced in a constant pressure, constant flow system such as what I used.
I was too afraid to use this system of purification and dioxygen from the industrial hydrogen kept getting into the flask. Ultra high purity dihydrogen solved this problem.
My suggestion to any replicators is to use a small volume sealed system right from the beginning. Fuse all wires to the cell material and when filled with solution and dihydrogen, fuse openings, do not rely on glues and other material. And please, remove all dioxygen possible, and do not anodise the cathodes for the early experiments. Keep the cathode pure metal. Use your intellect to generate dihydrogen separately with Al/HaOH to fill a balloon and use this to dilute the small volume of air in your cell. Then seal it permanently.
Profitis gave me lots to work with and I am thankful of that as I would not have got to this stage as quickly. Unfortunately I presently cant agree with him as far as the cells I tried are concerned. I cant at all comment on the oxygen karpens as I have not looked into these and don't really want to in the near future.
All I can say to investors in this technology is good luck!
Profitus, here is what I found, its in french and have no idea of what it says.
Please translate it and if its interesting I might give it a go.
Ok pomodoro I'm going to put a cork on the paranoia bottle from now on and act like a scientist is supposed to act,cool,relaxed and purely analytical,regardless of your results.I've found all of karpens documented work from 1900-1962 http://www.vasilescu-karpen.ro/ro/03inscrisuri/autor-r.html but they won't let me into the important 1948 document.they did however let me into the 1926 no.231 pp.70-72 document 'phenomenes semblant contredire la second de la thermodynamique,all about oxygen potentials there.they also surprisingly let me into the 1956 t.VI no.1 pp.29-33 document titled 'pila electrica cu hidrogen'.according to this last document karpen got a permanently stable 0.3v Pt(black)/Au under h2 in dil H2SO4. Interestingly enough that's exactly what the chinese got in H2SO4,0.3v. I can't open your file on my phone,it says 'unsupported'
Quote from: pomodoro on August 09, 2014, 12:43:53 PM
Thanks for your kind words MarkE.
I've worked as a chemist for 24 years but I am not an expert electrochemist. Now let me admit that electrochemistry upto 3rd year university level is about where it stops for me. Any more , such as some of the heavy stuff in the paper I posted is above my level of understanding. It would take a person with a phD in electrochemistry to really understand every aspect of such research.
Although a scientist I do occasionally look an non conventional theories with an open mind. The Karpen pile popped up on some random google search and I took a liking to it, simply beacuse it involves electrochemistry and I was able to gather the required gear.
I understand that there are occasionally massive egos and other obstacles in this field, but I focussed on the task at hand, nothing more.
I seem to detect that in this Karpen field of study, on this site, there have possibly been heated discussions, but I have not at all bothered to search or read any other posts, except for this thread, so I still don't know what exactly Profitis or others has said and I dont feel like bothering to read.
So, as you have seen, there were some goofs, some great initial results and finally some not so great ones.
I however am completely satisfied with myself, that I learned from the initial mistakes and the last unsuccesful experiments were indeed correct.
In electrochemistry, dioxygen is a real problem. Any dihydrogen really needs to be passed over very hot copper turnings or powder before being introduced in a constant pressure, constant flow system such as what I used.
I was too afraid to use this system of purification and dioxygen from the industrial hydrogen kept getting into the flask. Ultra high purity dihydrogen solved this problem.
My suggestion to any replicators is to use a small volume sealed system right from the beginning. Fuse all wires to the cell material and when filled with solution and dihydrogen, fuse openings, do not rely on glues and other material. And please, remove all dioxygen possible, and do not anodise the cathodes for the early experiments. Keep the cathode pure metal. Use your intellect to generate dihydrogen separately with Al/HaOH to fill a balloon and use this to dilute the small volume of air in your cell. Then seal it permanently.
Profitis gave me lots to work with and I am thankful of that as I would not have got to this stage as quickly. Unfortunately I presently cant agree with him as far as the cells I tried are concerned. I cant at all comment on the oxygen karpens as I have not looked into these and don't really want to in the near future.
All I can say to investors in this technology is good luck!
Pomodoro thanks for all the work and information. It is always possible, although often extremely unlikely that something exceptional will be discovered. I have no problem with people checking out seemingly crazy ideas. Ultimately carefully conducted experiments reveal the truth bit by bit. Profitis ideas are no different. There is always the possibility that he is onto something real. The big problem with his ideas so far is that he has often claimed that his ideas are solidly supported by established text books, but has routinely failed to cite any specific such references, or other evidence that support his ideas. Your experiments are a negative that adds to the weight against his ideas. It doesn't mean that he ultimately is wrong, but he now has more to account for than ever.
What metals/combinations are mentioned in your document pomodoro
Can't open rar archives? Man you need a real PC!
Or a phone upgrade.do you have any gold foil or wire lying around the lab pomodoro
No gold. I might be able to plate gold. Look I'm willing to try one more test, just one and it needs to be something related to these hydrogen cells and that is documented as being done by karpen. Are the above docs any good. What hydrogen cell is being talked about and what voltage or current did he get. No more fooling around with un documented systems.
You read my mind pomodoro (-:. Yes absolutely strictly along the lines of successful document tests from now on.my french really sucks but I could make out that pressure tends to raise potentials in hydrogen capsules.he got about 0.160v between black and smooth Pt at normal pressure and 0.7v under pressure if I'm not mistaken.he revealed nothing about other metals that I can make out there.the 1956 document is of extreme interest because it specificly names gold,which is also what the chinese tinkered with.I suggest gold plated onto glassy carbon surface(non porous) and afterward briefly etched in aqua regia.a hot boiling rinse in sodium carbonate sol will be required after etch to remove adsorbed chlorine gas and HNO3.you will have to plate quite thickish.I suggest the use of ammonium sulfate for electolyte in the karpen battery as opposed to the sulfuric which they used.ammonium sulfate is mildly acidic and has the advantage of lowering surface tension in solution much like bases do(its solution wets surfaces).dilute sulfuric acid does not wet surfaces.
You will have to be extra cautious about air leaks this time because O2 potential drasticly larger in acidic solutions.
The chinese after 10months playing with a sealed Pt(black) and smooth gold got an totaly stable 0.3v in H2SO4 aquaeous.other electrolytes they got higher or lower voltages.they got stable volts with Pt(black) vs Pt shiny too.
Neither karpen nor the chinese mentioned anything about current.that is up to me and you to maximize.
Well the pt black vs pt I can do back at work with no more expense. What conc sulfuric , hydrogen pressure and expected voltage did the Chinese get. I really want to replicate this cell as close as possible to the smallest detail. I would personally only expect ultra small voltages only. If you are worried about secrets then send the exact details to my email and all I will report here is if it worked or not without exact details.
I'm going to reply to that just now pomodoro.
While I'm waiting on profits, anyone know French and can translate the 3 pages?
Quote from: pomodoro on August 10, 2014, 08:37:04 AM
While I'm waiting on profits, anyone know French and can translate the 3 pages?
if you have them in non-image form.. can feed to translate.google.com
Leave the Pt(b)/Pt alone pomodoro.do the Pt(b)/gold setup please and report only voltage here(not current) in the same manner as karpen did and as the chinese did.
Do this setup in the gadget at atmospheric pressure please and with ammonium sulfate(1M) not H2SO4
Here is the carbon electrode I'll be using.
Test number 01
Pd/Pt (my best electrode) -
Air -
magnetic teflon coated stirrer -
Polished, Ethanol washed,Glassy Carbon electrode (note only a small area is the carbon black body is plastic) -
1N A.R. Sulfuric Acid in MilliQ purified Water.
Purpose of this test is to see how it behaves in air. Cell will be shorted out for 12 + hours
Video shows emf of fresh cell, Pd/Pt electrode connected to ground termnal, ie: carbon is negative 50 mV with respect to Pd/Pt.
Impedance of meter is 10^12 ohms, electrode processes should reach equilibrium, however any tiny impurity on electrodes will affect emf until cell is shorted for a long period of time to reduce/oxidize them.
Nice. Pt/glassy C in air followed by Pt/glassy under H2 pomodoro? Followed by gold coat in air vs H2?
Have a look at the monster overpotential of glassy C vs Pt for h2.. 2v! http://en.m.wikipedia.org/wiki/glassy_carbon
My prediction of this karpen oxygen cell is that there will be no voltage difference at all between the dissimilar electrodes when I disconnect the short in hours time . Karpen and Profitis would probably disagree.
This is an ultra easy experiment almost anyone can do, the electrodes are very inert, the only redox couple existing in equilibrium is 2H2O<-> 4H+ + O2 +4e-. This will have the highest current density on both electrodes. There is no hydrogen, so the other water redox reaction has no influence. Its happening on both electodes, oxygen pressure is constant, proton concentration is constant, The kinetics or rate may be different, but the potential by nernst is the same.
Please comment on this, anyone is welcome, before I video tape the event.
Saying that there will be no potential difference after long rest is like saying that there is no potential difference between Pt and carbon pomodoro.let them rest for one hour after disconnection.
Quote from: profitis on August 11, 2014, 02:54:21 AM
Saying that there will be no potential difference after long rest is like saying that there is no potential difference between Pt and carbon pomodoro.let them rest for one hour after disconnection.
So you are saying that after letting them for a few hours after the short is removed, you expect a potential difference to develop? Lets be clear about this Profitis, people need to understand exactly what we are doing and mean by our words. Thats why I've stated as clearly as possible what I have done in this experiment There is no conspiracy at work here, anyone interested needs to replicate these tests for themselves. Not too hard when just air is needed.
Of course pomodoro.do you think that a anodized carbon rod retains oxygen gas indefinitely? Impossible.the gas diffuses away,electrolyte wets surface.atomic O recombines into O2 and diffuses to where the pressure is alleviated.Its very small v anyway its not importante.leave it for an hour before measurement.
Gas in excess of equilibrium electromigrates(travells) up the cathode to surface.RT/nF ln P1/Psurface
Karpen's cell is an intermittant run thing... didn't it have a motor and a switch between two separate cells to allow a relaxation time?
Recently remembered electrets; which like magnets retain a permanent magnetic field, electrets retain a 'quasi-permanent' electric field... but if they're hooked into a circuit, they will instantly dissapate any charge they have, since they are also very high resistance/impedance.
https://www.youtube.com/watch?v=1DR-tTU8uIM
(This is the guy that was experiementing with dry-cells.. of various configurations)
and kinda disrelated; but entertaining; he made a wall of electroscopes :) But the electroscope he used to measure the electret.
https://www.youtube.com/watch?v=iD6FW8MRUXk
Electrets are often high voltage ultra low current things...
Although.... capacitors are also made with electret-like materials in balances with normal capacitive materials...
https://www.youtube.com/watch?v=K1CjN2I7YeM
But, if they're put through an inductor, for instance, then they would get repolarized oppositely...
they are also referred to as ferroelectric http://en.wikipedia.org/wiki/Ferroelectricity ; although 'electricity' is a misnomer really.
But; if such a cell could be made, it would have to be applied intermittently to a circuit, like a magnet... thereby requiring external physical work to make it do work...
http://en.wikipedia.org/wiki/Electrophorus ; uses an electret to apply a charge to a capacitive plate that can then be applied to a circuit for instance...
I dunno...
Yes d3,all karpens are intermittent.a certain amount of time is required to reboot.it was about 1 or 2 seconds between gold and platinum in karpens motor.if you shortcircuit karpens battery for an hour it will need an hour to reboot.the nickel-MnO2-KOH-air karpen in the vid below gives some idea of time required between bursts for a tiny battery.a larger battery will work with much shorter delay
Quote from: profitis on August 11, 2014, 05:59:55 AM
Of course pomodoro.do you think that a anodized carbon rod retains oxygen gas indefinitely? Impossible.the gas diffuses away,electrolyte wets surface.atomic O recombines into O2 and diffuses to where the pressure is alleviated.Its very small v anyway its not importante.leave it for an hour before measurement.
I agree but what does it have to do with the current setup? A Pt electrode at same depth as the C electrode. No pressure differential exists between them, thus emf is the same on both C and Pt, hence no voltage recorded on the voltmeter.
Do you not agree with this?
From your previous post I understood that you meant that the Pt itself will have a different potential to the C when dipped in the electrolyte, not due to the oxygen/water reaction, but because of their different elemental makeup?
You can make a karpen with 2 Pt electrodes pomodoro,one blackened,one shiny,one on surface one below surface like I described near the beginning of this thread.you get a perpetual 50microamps/cm2 bursts like that.platinum will adsorb a different quantity of gas than C will straight from air and hence will have different v than C even if both submerged.elemental platinum voltage is different from C's voltage but you will hardly register it(picoamps).you can say that they have electrostatic voltage in this case and will effect O2 potentials via the NEMCA effect(google nemca pt o2)
If your Pt was a little higher above electrolyte you would get somewhat more disparity between electrodes pomodoro.if you add ammonium sulfate you will get still more disparity because then the electrolyte will wet surfaces
So as a guess what would you expect the voltmeter to read after I allow the electodes to equilibrate for 7 hours tomorrow?
I have no idea pomodoro but there will be something there.if you had used platinum(black) cathode(touching surface) and etched platinum anode(submerged) I would without a shred of doubt say you are going to get the same voltage tomorrow as today.carbons are dicey and clingy which is why I wanted you to coat with gold.
Don't worry, the gold will come. Well I also think there will be some difference, but very small. What if gold was plated what then?
Lemmeputit2uthisway pomodoro,if your gold is adequately plated or if you use pure gold foil you'l get a voltage which will stubbornly absolutely refuse to go away.make sure you use ammonium sulfate plus sulfuric for wetability if you do this.
Now one last grilling profitis, before the gold, I'm going to put this cell under hydrogen, I still think there won't be much voltage difference between electrodes, what do you think?
You will get a voltage.that is due the NEMCA effect.how long it will take to recover I don't know but it absolutely will recover to some stable reading. You should never show voltages here that haven't been shorted FIRST then adequately rested because that is their true equilibrium value.that voltage that you showed in your last video is in fact meaningless because that was before shorting.hydrogen dissolves in platinum,it does not dissolve in carbon although it adsorbs loosely with it hence there will be something.with gold here you will without a doubt get something stable and permanent.gold does not dissolve h2
OK I shall disconnect short tomorrow and show the voltage after some hours. Hydrogen will then be pumped through while shorted. I'll still go for roughly the same voltage on Pd/Pt and C even with hydrogen. I reckon all the catalytic Pt electrode does is equilibrate ultra fast, the C will have a much weaker exchange current , so its potential will initially also depend on any other contaminating couples, but once those reactions are exhausted the same potential as the Pt will develop. I actually hope I'm wrong BTW.
Next post will have the result of the disconnection and rest phase for this oxygen karpen.
Ok before you do any hydrogen experiments or further oxygen experiments there is one setup I will insist that you do to prove your loyalty to science and to the overunity crowd pomodoro.it requires platinum(black) and platinum etched under air in Either acid or base.are you willing to do this dastardly simple experiment( you have all ingredients at hand)
When you show on camera the above experiment(Pt black vs Pt) result it will render all of what you just said above null and void.you cannot possibly tell us that platinum vs carbon or platinum vs gold will die out if platinum vs platinum works like a bomb
Quote from: profitis on August 11, 2014, 11:30:07 AM
Ok before you do any hydrogen experiments or further oxygen experiments there is one setup I will insist that you do to prove your loyalty to science and to the overunity crowd pomodoro.it requires platinum(black) and platinum etched under air in Either acid or base.are you willing to do this dastardly simple experiment( you have all ingredients at hand)
What are the exact details of this mother of all tests? Isn't it supposed to be shiny vs black?
BTW Im not going to do any tests if they require electrolysis, these will of course show hydrogen overpotentials!
I've just unshorted the cell, after 18 hours and will report hourly emf of cell. I'll keep modifying this post rather than creating new one, so keep coming back here for the updates.
negative value means C is more negative than the Pd/Pt
Time EMF
0 - 0mV
1hr -1mV
2hrs -8mV
3hrs -12mV
Voltage does change very slowly. Decided to end experiment here, now passing UHP hydrogen through exacltly same setup. Cell is shorted out
Some positive news., I've been going through text books and found a chapter that indicates that a Pt /C cell CAN act as a power source albeit at a very low current. Have a look at the attachment, Pic A11, is the cell as a power source, at zero volts (shorted) there is a miniscule current flowing. This cell is deaerated, however so the rest voltage is somewhere between the two water redox couples, any oxygen such as in the cell I'm testing, would shift both to the same potential of the anode. Hydrogen would have do the same, but there will be a potential difference. Ummm, looks like hydrogen will be pumped in soon.
That is a good find.
This cell setup pomodoro.this cell I have done hundreds of times.it has a most stubbornly persistent oxygen potential difference and 50-100microamp/cm2.use NaOH or ammonium sulfate solution.both electrodes are same metal so it proves beyond all doubt a very definite participation of oxygen gas spillover.
Thats easy to do. I need to prepare platinizing solution, so I can't do it straight away, but soon..
Right now UHP hydrogen is being used in exactly the same cell I tested with Air, nothing was moved. Keep an eye on that post as I update voltages in about 16 or so hours.
The above Pt(b)/Pt/O2 cell setup shoulve been done ages ago,my bad (-:
Don't you have any platinized platinum lying around pomodoro.this is THE most important experiment for O2 cells by far and it is one that I KNOW works everytime with labgrade foils.
Which electrode was the cathode in your Pd/glassy C/air test result above pomodoro
Quote from: profitis on August 12, 2014, 04:01:13 AM
Which electrode was the cathode in your Pd/glassy C/air test result above pomodoro
Cathode was the Pd/Pt, slightly more +ve than the C.
No platinized Pt, it dissapeared when I heated the Pt in a bunsen! Been using Pd black in all my experiments.
I guess I should be stopping the stirring in these experiments when I take voltage readings, otherwise the different gas concs are getting averaged out?
Good.now we will see if that potential switches polarity under H2..(!)
Yes.halt all stirring because it interferes.also skeptics love to blame it.the slowed diffusion rates of ions or gases can work to our advantage in some cases
Quote from: MarkE on August 12, 2014, 03:24:24 AM
That is a good find.
Yes I was quite surprised myself. The book is " Electrochemistry, The Basics with examples" Christine lefrou.
The slower kinetics for the hydrogen couple on the carbon give it a wider curve, so rest potential is more negative than that of the Pt. The upward part of the hydrogen couple is not shown on these plots, as they are for deaerated solution.
I think using silver as a cathode was done too early in the piece. Let's see what happens when the cell is allowed to recharge in a few hours...
I think silver was not done too early in the piece pomodoro.I think silver was simply not given sufficient time for resting inbetween.the dual-platinum/O2 experiment wouldve set the record straight for this thread long ago.better late than never
As Pomodoro wraps up his experiments what you should really be thinking about is how you can state a hypothesis that they have tested that is relevant to your claims. Then you can formulate an argument as to how the tests falsified, supported, or generated a null result against your claims.
Who said pomodoro is wrapping up experiments @mark E? We are just now getting it right..
Quote from: profitis on August 12, 2014, 04:07:04 PM
Who said pomodoro is wrapping up experiments @mark E? We are just now getting it right..
Pomodoro has said so.
Before or after the latest results @mark E
Profitis, you are perfectly capable of reading the thread. Pomodoro has written several times now that he intends to wrap things up.
Before or after the latest results @mark E
Profitis, if you believe that Pomodoro has changed his mind, then it should be simple enough for you to point to where he has said he has said as much.
Be-fore..or af-ter the latest results @mark E..
Profitis Pomodoro is going to do as he sees fit, and he has stated his intentions. You can observe those statements directly in this thread. You may believe or just hope that he will change his mind from what he has stated as his intentions. Since you obviously don't have any statement you can point to, why don't you just ask him if he has changed his mind or is reconsidering wrapping up as he has stated is his intent?
When you publicly substitute assumptions for direct observation, it raises questions as to whether you do the same thing in the laboratory.
@mark E it is you who is assuming that pomodoro will dissapear after the latest positive results..not me.
Why even discuss the theoretical impending dissapearence or re-appearance of pomodoro @mark E..madness man
Profitis, If you think that sticking to the facts makes me a "madness man", then so be it. You might want to consider how your behavior may or may not affect anyone's interest in engaging you.
I have not discussed appearance or disappearance of anyone. Once more you've pulled some idea out of the blue. I have noted the fact that Pomodoro has stated his intent to wrap up his experiments. I have noted that it is in your interest to formulate a hypothesis relevant to your claims that you feel his experiments address. I have no idea and do not presume to guess whether or not, or for how long Pomodoro might stick around once he is done.
Guys I will leave, but I want to make sure what I do leave behind are not the results of badly executed experiments. When the hydrogen runs out I am done as I can't use it for anything else and can't get a refund for what is left.
Quote from: pomodoro on August 12, 2014, 08:12:53 PM
Guys I will leave, but I want to make sure what I do leave behind are not the results of badly executed experiments. When the hydrogen runs out I am done as I can't use it for anything else and can't get a refund for what is left.
Pomodoro, that is very reasonable. Can you venture about how many more hours endurance H
2 that you have left?
Its not in my interest to formulate anything @mark E.the goal is to build an oxygen concentration cell and show how the textbooks are correct with the nernst equation. (I said madness,man not madness-man)
Pomodoro.please do not leave without doing the cell setup with 2 platinum electrodes. That is the definitive test
Quote from: profitis on August 12, 2014, 08:17:50 PM
Its not in my interest to formulate anything @mark E.the goal is to build an oxygen concentration cell and show how the textbooks are correct with the nernst equation. (I said madness,man not madness-man)
You are playing directly to Sarkeizen's predictions. Pomodoro has gone to substantial expense and effort in order to entertain your ideas and has shown some interesting experiments, and I am grateful that he has conducted them. If the sum total of your ideas is as it presently appears that the Nernst equation amounts to a violation of the Second Law then experiments were not necessary. You would first be on the line to show how violation of the Second Law would follow from validity of the Nernst equation.
As to you wrote, this is it:
QuoteQuote@mark E..madness man
I really don't give a hoot about childish insults. I do think it is odd that you deny what you've written.
Pomodoro.if you build the duo-platinum oxygen concentration cell for us you rescue this thread
Lol @mark E.your crazy.I invite any viewers to build my last diagramed dual platinum(black)/platinum smooth air cell in NaOH or ammonium sulfate electrolyte to prove to themselves what's really going on on this thread.
Probably a weeks worth of H2. Wasted a heap last night as the flow increased by itself. Electrolyte level dropped below electrodes, so will need to wait another day for the results of the hydrogen test...
:(
I'm busy doing other real work at the moment, so this research will take its time folks.
And this video to destroy all of mark E's fantasies of the second law thermodynamics. A thick etched platinum wire is ANODIC,that's right my friends,anodic vs nickel-black exposed to air at surface of NaOH electrolyte.the blackened nickel(+) retaining greater O2 adsorption than the submerged platinum(-) giving rise to an oxygen concentration nernst value on the v-meter
Here's a closeup of the above o2 concentration cell components
Quote from: profitis on August 13, 2014, 12:53:56 AM
And this video to destroy all of mark E's fantasies of the second law thermodynamics. A thick etched platinum wire is ANODIC,that's right my friends,anodic vs nickel-black exposed to air at surface of NaOH electrolyte.the blackened nickel(+) retaining greater O2 adsorption than the submerged platinum(-) giving rise to an oxygen concentration nernst value on the v-meter
Assuming for a moment that the experiment in an apparently dirty bottle cap was not polluted, and that the materials are as you represent them, how is it that you contend that what is shown in the video violates the Second Law of Thermodynamics?
Nah it gives perpetual power @mark E(same like karpen cell). viewers,varsity students,scientists can easily replicate this one.try maximize with larger electrodes.it won't work under pure argon or nitrogen by the way,only o2/air
Quote from: profitis on August 13, 2014, 01:55:28 AM
Nah it gives perpetual power @mark E(same like karpen cell). viewers,varsity students,scientists can easily replicate this one.try maximize with larger electrodes.it won't work under pure argon or nitrogen by the way,only o2/air
Is it your assertion that:
The cell operates without generating any reaction products from the inputs? If that is not your assertion, then on what basis do you claim that it: "gives perpetual power"? Is it an assertion that a concentration changes indefinitely while remaining unbalanced indefinitely? Clarification is needed to determine if you are making a claim against the First Law, or the Second Law.
It doesn't work under argon or nitrogen,only air or oxygen,which means o2 is without a shred of doubt involved in its electrode reactions.this is to be expected because the oxygen concentration is much larger at the nickel than at the platinum.after o2 concentrations are leveled out on discharge,opening switch allows recharge and re-distribution of original oxygen concentrations spontaneously. 100% reversable catalytic oxygen spillover from nickel onto platinum in this case.against kelvin rule.
Also note that corrosion current is impossible.according to standard table of potentials nickel must corrode by a exponentialy huge margin.
I can give you more such examples of spontanteously- reversed galvanic couples if you want @mark E
Quote from: profitis on August 13, 2014, 02:35:46 AM
It doesn't work under argon or nitrogen,only air or oxygen,which means o2 is without a shred of doubt involved in its electrode reactions.this is to be expected because the oxygen concentration is much larger at the nickel than at the platinum.after o2 concentrations are leveled out on discharge,opening switch allows recharge and re-distribution of original oxygen concentrations spontaneously. 100% reversable catalytic oxygen spillover from nickel onto platinum in this case.against kelvin rule.
Is it your contention that the oxygen concentrations return to their disparate levels without application of outside energy?
Electrochemical entropy will squash gas from the cathode onto anode at expense of temperature entropy on discharge.spontaneous heat inflow from ambient without need for temp gradient will disperse gas on recharge. You want to make as much power density as you can to be able to test these cells adequetly against the 2lot.
For power density on an o2 karpen I suggest the MnO2 pyrolusite/ nickel(blackened)/NaOH/air variety,easy to make and cheap.in this case nickel is your anode(submerged)
Quote from: profitis on August 13, 2014, 04:11:41 AM
Electrochemical entropy will squash gas from the cathode onto anode at expense of temperature entropy on discharge.spontaneous heat inflow from ambient without need for temp gradient will disperse gas on recharge. You want to make as much power density as you can to be able to test these cells adequetly against the 2lot.
So, is it your claim that the materials in the cell operating at the same temperature as the surroundings absorb heat from the surroundings, and in doing so generates a disparity in the O
2 concentrations that exist in the vicinity of each electrode?
Quote from: profitis on August 13, 2014, 02:48:30 AM
Also note that corrosion current is impossible.according to standard table of potentials nickel must corrode by a exponentialy huge margin.
But now it has a film of nickel Hydroxide, so the tables are no longer valid.
Yes @mark E.gas is dispersed,heat absorbed,potentials re-constituted.its an EQUILIBRIUM POTENTIAL DIFFERENCE.karpen gave same explanation.
Exactly @pomodoro.nickel is so inert in alkali it can go cathodic to platinum.this justifies its use for oxygen evolution in the MnO2/nickel setup where it is anodic
These cells have tens of thousands years shelflife.that in itself is violation of 2nd law.they are negentropic
Quote from: profitis on August 13, 2014, 05:01:02 AM
Yes @mark E.gas is dispersed,heat absorbed,potentials re-constituted.its an EQUILIBRIUM POTENTIAL DIFFERENCE.karpen gave same explanation.
Over what temperature range does your preferred cell chemistry supposedly pull heat from the surroundings?? Will it work between 50C and 0C? 25C and 10C?
So long as the electrolyte does not freeze and crystallize it should be fine
Quote from: profitis on August 13, 2014, 05:20:34 AM
So long as the electrolyte does not freeze and crystallize it should be fine
So do you agree to 10C and 35C as a viable working range?
Don't know @mark E.It must be tested to its limits.I'm just working at average capetown temps summer through winter it works fine.
So if the claim is true, do you agree then that a black box containing the materials in thermal isolation will:
1. Output a minimum quantity of energy when loaded externally.
2. During the output phase demonstrate a movement towards equalization of the oxygen concentration in the vicinity of the two electrodes.
3. Recover from delivery of said energy in a defined period of time after the load is disconnected.
4. During the recovery, the oxygen concentrations at the two electrodes will become disparate.
5. During the recovery, cool down internally.
4. Not exhibit degradation of any of the internal materials cycle to cycle.
@mark E.yup. Guys with labs must build it with solid pyrolusite chunks or pure Mno2 chunks.chunks,not powders,not platings.etched in HCl for surface area.solid chunks pyrolusite is a good conductor.you can order pyrolusite tumble-stones from gems/minerals suppliers on the net. These chunks give highest power density(for an o2 karpen)
So you beg me to not bother with the oxygen karpens when I came on here and now you keep babbling on about some cowpat that gives power for a million years. You are a strange man profitis
Given the difficulties associated with hydrogen containment yes I shouldve just gone with the air flow first pomodoro.its not too late to make ripples here mate.we can make micro-history with a full-blown double plat-air device what say you pomodoro. This time we get desired results correct first via pms before hopes goes down the drain due to error/delays/disputes what say you?
Pomodoro seems to have managed to get the hydrogen set-up free of O2 intrusion that you insisted upon and his results so far have not supported your hypothesis. I think Pomodoro is perfectly justified in expressing his frustration that the tests you insisted upon have consumed a great deal of his time and money, and that now you want to go in a completely different direction on his time and nickle. What hard data can you produce that would motivate Pomodoro or anyone else to pursue further test of your ideas? What is there to show that what you propose now would be anything more than the sort of "tinkering" that Sarkeizen has so vocally criticized?
Hard data? Lol @mark E.do you actually understand what I'm asking pomodoro to do.I'm asking him to shove two platinum electrodes into base or acid and get perpetual power from it in a very definite direction,cathode ontop,anode submerged.in line with what we expect from the nernst equasion and oxygen concentration disparity
Profitis, this thread documents very well what you have and have not done. If what you ask of Pomodoro is so trivial and the results so important, one might rightly point out that you should have done this long ago. Yet, the best we get from you is a dirty bottle cap.
Let him decide @mark E.the viewers are really keen to see if it will work (-:
Quote from: profitis on August 13, 2014, 05:43:40 PM
Let him decide @mark E.the viewers are really keen to see if it will work (-:
I don't attempt to speak for Pomodoro. Again, if what you ask is so trivial and so significant why is it that you have not done it? Why hasn't anyone else done it?
I've done it,hundreds of times.just want to know if he wants to do it too (-: what's the big deal @mark E?
Quote from: profitis on August 13, 2014, 06:02:28 PM
I've done it,hundreds of times.just want to know if he wants to do it too (-: what's the big deal @mark E?
The big deal is that: You have made extraordinary claims that you have not evidenced. You have insisted that certain experiments if done by others would support your extraordinary claims, but when Pomodoro went to great lengths and expense to conduct experiments that you dictated, the experiments failed to support your claims, and now you insist that different experiments are needed. It should be plain to see how frustrating it should be to Pomodoro that because he gave you some credit he spent a lot of time and money on what you now declare was pointless. It should be plain to see that what you have dropped your credibility to a new low. I can't imagine a prospective employer seeing how you have conducted yourself giving you any serious consideration for a position.
Are you saying that the two-platinum system will not give power and current @mark E
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(http://www.overunity.com/Themes/default/images/post/xx.gif) Re: KARPEN PILE (http://www.overunity.com/14660/karpen-pile/msg414094/#msg414094) « Reply #440 on: August 12, 2014, 05:31:54 AM » Quote (http://www.overunity.com/14660/karpen-pile/435/post/quote/414094/last_msg/414282/)
BTW Im not going to do any tests if they require electrolysis, these will of course show hydrogen overpotentials!
I cant modify the original message, so I'll keep pasting the original, with additions.
-----------------------------------------
Air Karpen Pd black on Pt vs Glassy Carbon in 1N Sulfuric Acid.
I've just unshorted the cell, after 18 hours and will report hourly emf of cell. I'll keep modifying this post rather than creating new one, so keep coming back here for the updates.
negative value means C is more negative than the Pd/Pt
Time EMF
0 - 0mV
1hr -1mV
2hrs -8mV
3hrs -12mV
Voltage does change very slowly. Decided to end experiment here, now passing UHP hydrogen through exacltly same setup. Cell is shorted out
-------------------------------------------------
Hydrogen Karpen, same setup as above, but flushed with constant UHP quality hydrogen
Notes: Pd/Pt electrode in 1N H2SO4 now becomes essentially the well known NHE electrode. Normal hydrogen electrode found in all text books. Very fast response / kinetics. Large exchange current . In other words, any stray oxygen gas has very little effect on its voltage as it is swamped by the fast hydrogen/proton reaction. We need to focus on the other electrode to explain strange behavior. Forget about this electrode!
As soon as hydrogen was introduced, the voltage immediately rose to a healthy +800mV. The carbon becoming the cathode, with reduction occuring at its surface. This is very easily explained by remembering that any residual oxygen has little effect on the Pt electrode but will give rise to a mixed potential at the Carbon. The hydrogen/proton kinetics are very slow at the carbon, so its potential will be a mixture of the oxygen redox and the hydrogen redox potentials, the onw with faster kinetics will dominate the reading.
Anyone repeating these experiments must remember that oxygen, or oxides on the surface will fool you into believing you have a huge potential.
After a few hours of shorting out the terminals, to reduce any oxygen reaching the Carbon, the short was removed and the voltage monitored, here are the results as measured with a 10^12 ohm electrochemistry style voltmeter.
Time mV
30 secs +26
1 min +40
5 Min +96
10 min +118
40min +137
70 min +147
This is much slower than when the cell is shorted immediately after the hydrogen is first passed, an then unshorted. In this case the voltage rose to +800mV in 15 seconds!
eighteen hours of shorting out later, and here are the results
Time mV
30s +8mV
1 min 13 mV
12 mins +70mV
50 min +122
1hr 50m 134
2h:50 min 141
4h:20 min 146
5hrs +146
Conclusion, after equilibrating, cell seems to show a potential difference of 146mV, with the carbon electrode taking on a positive voltage.
Unless the cell is sealed completely, it is impossible to know if a trace of oxygen from the hydrogen which is being constantly bubbled through the cell has any influence on this voltage.
less than 0.1uA flows when shorted.
I then deliberately use a 6v cell and placed it across the electrodes for 3 seconds , visibly producing hydrogen at he carbon and oxygen at the Pt.
The voltages across the electrodes are now -1200mV, I'm planning to see its recovery
Yes, this forum locks out changes after awhile. I think it is about a day.
0.1uA is a pretty small short circuit current.
Excellent result @pomodoro. Proves a dead-stable 0.146v.it sounds about right for carbon systems.the chinese only got about 0.07 v for a different type of graphite vs Pt not Pd.you see now clearly the importance of shorting,then relaxing, before getting its real voltage
The one thing I don't like about carbons are that they tend to cling to gases quite long after a rest period.van der waals forces hold onto gas quite stubbornly,I wonder what diamond would do.
You should retry your industrial hydrogen vs uhp in the same setup,same waiting period and see if it differs.you should also try with an electrolyte additive that wets surfaces like ammonium sulfate
adequately gas exposed palladium would remove traces O2 from your industrial h2 by instant catalytic recombination H2+O2>H2o.or you could just float some platinized asbestos fluff ontop electrolyte.
Voltage recovered back to +146 but then dropped to 8. Even opening to oxygen only raised it back to 150. Something screwed up, I think, after passing the 6v. no time to check today. I will try plating gold for the next test.
carbons are very unpredictable pomodoro it takes long time to equilibrate due to van der waals.tell me something before you plate gold,is that glassy C patch rough or smooth and is that 0.1microamp that mark E is refering to at the base of the discharge curve or top
Smooth. There was basically no current out of this. 0.1 I saw just for a split second. It did discharge because the volts dropped to zero. Area is quite small, diameter is probably 3-4 mm. I have no more industrial h2 for other tests.
At least you proved that the chinese laborarory tests are consistent with reality.smooth glassy carbon at 4mm is minuscule surface area but it should be ok to make out voltages.plate that gold thick pomodoro,we don't want any interference from the underlying carbon.use wetting agent,ammonium sulfate added to your h2so4 for this next test.sulfuric sol does not wet surfaces well.
Make sure that your gold-plating solution has wetting properties otherwize we'l get micro-patches exposed carbon
I think your palladium was slightly poisoned after you induced electrolysis btw pomodoro.a tiny bit sulfate ion reduced all way to H2S creating that dip anomaly.this is why I'm against any hydrogen production from sulfates. H2SO4 + 8H+ + 8e- > H2S + 4H2O. 0.3v
I need to re palladise my electrodes, cells, even in alkali, are not responding well when oxygen is reintroduced. Don't ask me how anyone can seriously test these cells at home. It seems oh so easy on paper, but so much goes wrong.
I may end up using some clear plastic test tubes to make fused electrode, sealed versions of the Pd/Pt NaOH Cu hydrogen cell and call it quits if it dies.
Try cathodizing hectic in NaOH to drive sulfides back into solution and restore activity in the same manner as silver is cleaned from Ag2S pomodoro.use a cheap graphite anode
Don't call it quits before you have built and tested my suggested pt(black)/pt(etched) air/o2 karpen to fanaticaly convert you into a karpen believer.
Don't worry I promise to do that before I leave. Look I don't disbelieve anything, let's let a perfectly executed experiment determine the truth. So far I'm skeptical but not looking to destroy the theory.
Glad to hear it. Its fail-proof,works everytime (-:
This test shall be done after I finish with the hydrogen. What voltage differential do you expect to see.
Similar voltage to my pt(-)/Ni(+) air experiment.anything between 0.1-0.2v. A lot depends on your platinizing skills.if you use manufactured platinized pt foil definitely 0.1 and up.use high impendance v-meter for stable reading or large pt foils with a normal digi v-meter.you'l get around 50micro-amp/cm2 in bursts.
Have a look in this picture.here is another spontaneously reversed potential against the standard table.2Ag + CO3-- >< Ag2CO3 + 2e-.. -0.47v (standard)/MnO2 + 2H2O + 2e- >< Mn(OH)2 + 2OH-..+0.05v(standard) .this is because O2 gas kinetics faster on MnO2 catalyst as opposed to silver catalyst.this will not work under argon.
And another spontaneously reversed potential against the standard table in alkaline solution.Pt + 2OH- >< Pt(OH)2 + 2e-..-0.15v(standard)/MnO2 + 2H2O + 2e- >< Mn(OH)2 + 2OH-..+0.05v(standard).this is again because of faster O2 forward kinetics on MnO2 catalyst than on smooth Pt catalyst.this will not work under argon.please note,for convention I ascribe a minus (-) sign to standard potentials below hydrogen and (+) to above hydrogen(0.0v)
Ever tried iron as a cathode in the hydrogen cells?
I've measured it as anode,results inconclusive,seemed weak.
Steel wool, large surface area.
Platinized platinum has higher work function than platinum smooth.although it concentrates o2 better than the smooth it releases o2 to electrolyte easier than the smooth,less tightly bonded to the o2 gas.quite perverse.
Etched iron even larger area
submerged nickel vs Pt foil in alkali an astounding 0.04v with the nickel as cathode(!)Not anode.
@sarkeizen.all hydrogen encapsulated experiments require excessive knowledge,skill and experience.all air oxygen experiments require none of the above.therefore we conclude all oxygen air experiments in this thread to be 100% consistent with karpen expectations and repeatable by anyone.
Here is my latest test. Massive surface area steel wool.
Steel wool , degreased in dichloromethane, etched iin dilute HCl, washed many times with deionized water.
Newly prepared palladized platinum, 1M NaOH , UHP hydrogen.
When initially fired up, volts rise to +500 mV wrt the Pd/ Pt electrode.
Discharge through meter is huge, peak well over 10mA, and discharge goes over many minutes at over 1mA.
A lot of this is due to any oxygen still in the cell and any oxides that formed on the steel wool. Cell is shorted now out for over 12 hours to force all oxygen and oxides to reduce.
Please see video of the very initial discharging. A followup will be posted after the overnight discharge.
The meter peg is impressive.
Attached are pics of a failed copper cathode Karpen. Somehow I could not get the copper to become cathodic. I tried both acid and alkaline electrolyte. Having the copper as anode , even with hydrogen around makes it difficult to rule out anything but the hydrogen being oxidized. I assumed the copper pipe contained other alloyed substances which are more easily oxidized.
Copper snail abatement tape for keeping snails off trees is available from the home improvement store garden section is rather pure and reasonably cheap.
I've never done the hydrogen cell before with iron as cathode,will be interesting to see result although I'm not expecting miracles with it(I'm expecting it to go anodic not cathodic).copper wire from a normal appliance lead is basicly purish copper.I simply use a single bundled etched(HNO3) strand of such wire as all my copper cathodes.you must be careful of alloys yes.brass and bronze are a no-go.pure Gold is the ultimate cathode material for scientific hydrogen spillover results in alkali or acid.
Pomodoro if you use pure gold as your cathode the chances of success go dramaticly up.use a big a piece as you can get.plate it thick onto etched silver
Mercury is next then I'm packing up. Gold plating on carbon no good. If these cells work I think cathode needs to be far deeper away from hydrogen. They only work due to lower activity of hydrogen ie concentration cell.
Intercatalyst spillover/nernst diffusion potentials pretty much the same thing manifesting pomodoro.let's say that your onto something with strict concentration cell theory and say that it is not violent spillover for example in the silver/palladium variety,then what we should actually be doing is allowing partial exposure of the silver cathode to hydrogen atmosphere within the device and upright position to allow for maximum upward electromigration of gas against depth-pressure after each discharge burst?? It might work.it has to work.indeed yor silver wire experiment should have worked for this theory.
Here's my own video evidence that fuel cell studies on oxygen spillover from MnO2 onto gold indeed is the case http://yadda.icm.edu.pl/yadda/element/bwmeta1.element.elsevier-f90154b1-a9e9-3857-b425-522244f423a4 .MnO2 is positive in voltage to pure gold foil here in this karpen setup.
Here's a closeup of the above experiment setup.both gold and MnO2 submerged under alkaline electrolyte.gas passage is via diffusion.this experiment will not work under argon,nitrogen.
Afer 18 hours of discharging the Iron cell slowly climbed up to -30mV after a few hours. Discharge was very weak. It became anodic.
And now, for the mercury karpen. Check the vid
So, the Hg ismuch like some of the earlier experiments.
Is this the end of your testing?
Dont know about the Hg till tomorrow.
The difference is that it is far away from the hydrogen up on top.
Wow! I love the speed at which that cell recharges pomodoro.your idea to bury the connecting wire under the mercury is novel.what electrolyte are you using?
I'm frightened of electrolyte seeping up the blue wire-jacket and overrunning the Hg potential but it looks good so far.
Discharging all traces mercury oxides off that mirror surface should happen within minutes
Quote from: profitis on August 21, 2014, 04:17:32 AM
Wow! I love the speed at which that cell// recharges pomodoro.your idea to bury the connecting wire under the mercury is novel.what electrolyte are you using?
Still 1m naoh.
Excellent.NaOH will wet surfaces completely.can you do me a favour quik pomodoro,disengage the short quik and tell me if the voltage still climbs please
Sorry I am at home. But 3 hours ago it reached 100 mv in 10 s and 200 in 30s
A good indication.is that blue wire buried all way down under the mercury
Quote from: profitis on August 21, 2014, 08:44:57 AM
A good indication.is that blue wire buried all way down under the mercury
Yep. Stripped section is bent at right angle. Plastic of wire practically touches glass base.
Great.guess which electrode is going to be the cathode in this pic.a tiny copper speck is on the carbon.the cell under nitrogen.
After 24 hours I unshorted the cell and saw what you will see in video hg.mp4
I stirred the magnetic stirrer for a while but there was no change.
Then I increased the hydrogen flow and got the result hg2.mp4.
And for a few days I will leave a shiny Pt electrode just above the mercury.
The volts is between the new Pt and the mercury. I expected this new electrode to be closer in potential to that of the mercury, so far (early days) it is even more negative than the Pd/Pt up on top.
Ok pomodoro.now leave that cell alone to rest 2 hours in order to re-equilibriate.I can see (as expected) that that voltage wants to climb allllll way back up.don't stir it,don't touch it,just get reading
Why did you jump the experiment pomodoro? It was indicative of success.
You jump too quickly between experiments brother.before conclusions can b drawn!
Quote from: pomodoro on August 22, 2014, 03:00:05 AM
After 24 hours I unshorted the cell and saw what you will see in video hg.mp4
I stirred the magnetic stirrer for a while but there was no change.
Then I increased the hydrogen flow and got the result hg2.mp4.
That is quite a difference.
Yeah its a difference mark E.it indicates that the increased vigour of bubbling shortened the time-span of palladium resaturation.in other words there was no saturation at the Hg cathode!!! Pomodoro shouldn't jump experiments,confusing.
My highschool science teacher wouldve beaten me up if I jumped experiments like that prior to conclusion.
Not jumping at all, I just added an electrode near the merury. Nothing changed. Want to see if the Pt changes voltage to near the Hg one. Current from the Hg is too tiny to be practical, but at least there is a large voltage there. I still have some hydrogen left.
Quote from: profitis on August 22, 2014, 04:29:42 AM
Yeah its a difference mark E.it indicates that the increased vigour of bubbling shortened the time-span of palladium resaturation.in other words there was no saturation at the Hg cathode!!! Pomodoro shouldn't jump experiments,confusing.
You could have always written out a proposed protocol at the beginning of the tests or anytime along the way. It's a bit late to start negotiating test protocol.
Not jumping pomodoro?You had to open the thing up and expose it to air correct? My teacher wouldve murdered me.the climbing rate of that voltage after 24hrs short-circuit was about 0.001v/second and was exceptionally likely to accellerate its climb over time.
The palladium/mercury experiment is therefore deemed by me to be a total success.the palladium has to be higher up just its corner touching the top of electrolyte for even greater voltage disparity and far more rapid voltage climb due to shorter resaturation timespan.
Quote from: profitis on August 22, 2014, 05:14:50 AM
The palladium/mercury experiment is therefore deemed by me to be a total success.the palladium has to be higher up just its corner touching the top of electrolyte for even greater voltage disparity and far more rapid voltage climb due to shorter resaturation timespan.
In that case I suggest that you write out your hypothesis, and then state how the experiment falsifies the null, or is at least consistent with the hypothesis proper.
Its very simple @mark E.the stirring/agitation ontop the mercury had no effect to accellerate volts climb after 24hr short.the increased bubbling agitation over the palladium obviously decreased saturation time,that's the time we were supposed to wait out in this experiment.that's where pomodoro went wrong ie.interference with the timespan for resaturation.the voltage climb directly after 24hr hour short was indicative of what was going to be revealed after 2 or 3 hours rest.total success in line with reversable hydrogen spillover theory, in line with nernst theorem, in line with overpotential theorem.
Profitis: I am not asking that you write a narrative to me. I am suggesting that if you believe that the experiments support your ideas that you state your hypothesis that you believe the experiments addressed, and then show preferably that the experiments falsified the null, or in the least that they support the hypothesis proper.
Right @mark E.the experiment proved beyond reasonable doubt a willingness for the palladium/mercury/NaOH/H2 battery to spontaneously self-recharge without outside interference in the same way that oxygen spillover devices do.let's see what pomodoros latest test reveals.let's wait for more data.
Ive leaned from these experiments to expect failure later on. In this setup, there is no real positive pressure as I am using the spout of the cylinder for the entrance of the wires. Its only a small gap but its still a gap and although the hydrogen is flowing out, some air could be coming in.
The mercury is quite deep in the cylinder and I would expect the bubbling hydrogen to purge a lot of the oxygen out but who knows. The upper Pd/Pt is succeptible to air and its strange behaviour in low hydrogen flow may be due to a little air entering the cylinder on top.
Lets see what the Platinum down there does. There is very little hydrogen dissolved in water but perhaps enough to for a couple with water on the Pt. Mercury dislikes hydrogen, so the activity of hydrogen is lower on its surface.
The reduction potential on the Pt shoud be around -0.83V for H2/H2O/OH- in 1M NaOH. This will be quite accurate in the cell.
that for Hg/Hg2+ is +0.85 but in standard conditions, so here it will not be that, but will be a mixed potential which will include the sum of the above hydrogen couple. how much influence any of these have on the actual potential will depend on their kinetics ie: current densities.
Any oxygen will raise its potential substantually.
If there is a positive outcome in a few days, when I got back to the lab, a sealed version will be made.
So in my books, it looks positive, although it has no power, but I will need to completely seal it to be sure.
I don't understand mr pomodoro.you choose to tell us about this airgap concern only now? And introduction of a second wire doesn't increase your chances of air inflow? and why are you getting the standard electrode potential for mercury in alkali completely wrong? It is exactly -0.098v for HgO + H2O + 2e- >< Hg + 2OH- with a thick paste of mercury oxide mixed in with the mercury,which as you know is totaly and utterly completely absent in your mercury metal.all invisible surface oxides should be virtually wiped out off that mirror surface in seconds on mere exposure to H2.forgive me but I'm going to be harsh with criticism
Please note mr pomodoro, I've already declared your mercury/palladium experiment a success.I want to see if you can follow up on this now.
Dear profitis no need to apologize. All criticism is more than welcome. If the cell looks good in a few days, then a version which will be completely sealed will be made.
Ok pomodoro you can handle it (-:. Work with me please.don't tinker.leave the tinkering until you are finished with live experiments.viewers get confused.our main focus was and now definitely is very specificly that palladium sponge vs mercury potential.anything else is distraction.
No problemo, I'll work on another bung design that will allow positive pressure like the previous setup.
Continuous flow please pomodoro.Make sure that the end exhaust pipe is under water for pressure and to act as oneway valve.I don't trust any static systems because they cannot purge airleaks. the ideal exhaust rate is about one bubble every 2 seconds.
Use a singlestrand jacketed copper wire for your mercury connection
Ok folks, this is my latest attempt at a profitis cell. We have the setup that you can see in the vid below. Triple distilled mercury is at the bottom of the cylinder. Above it is a magnetic stirrer which I might use later. In the mercury is a a copper wire, prepared as seen in the picture. Melted glue prevents any water from seeping up the wire strands.
Up on top is the palladized platimum electrode.
UHP hydrogen is bubbled through the liquid , and pressurises the space between the bung and the electrolyte, which is 1M NaOH (AR) in MilliQ water. The hydrogen comes out of the cylinder and bubbles through a water 'valve'.
The flow of hydrogen is higher than normal as I have just set the cell up and want to remove oxygen quickly. Its flow will be lowered later.
Voltmeter shows volts of mercury wrt Pd/Pt. Later cell needs to be shorted to make sure all reducible species are reduced by the hydrogen.
Success will achieved if tomorrow and even later, a healthy voltage still exists between the two metals.
Video is under this line.
Can you move the palladium sponge a bit higher up please pomodoro.just the tip touching electrolyte.it is impossible for this cell to not climb back up in voltage according to the monstrous overbearing power of that famous equasion: the NERNST EQUASION.
i could not move it up as it is compressed in its hole .
Anyway, have a look at the two vids, the first shows the equilibrium current after approx 18 hours of discharging. You also get to see the result of unshorting the terminals.
The second video shows the potential reached after 5 hours of letting it 'recharge'.
Impossible pomodoro.I reject this final 'recharge' result outright.you disconnect after 12hours and the thing immediately climbs at about 0.001v/second up til the 0.024mark before video blackout and you expect us to believe it settled at 0.033 after 5hrs?
Pomodoro pomodoro tsk tsk.remember when you said your going to with-hold any good info from publication? Naughty naughty (-:
Quote from: profitis on August 26, 2014, 05:02:49 AM
Impossible pomodoro.I reject this final 'recharge' result outright.you disconnect after 12hours and the thing immediately climbs at about 0.001v/second up til the 0.024mark before video blackout and you expect us to believe it settled at 0.033 after 5hrs?
You can always reproduce the experiment yourself and try to obtain a different result.
Mmm @markE.I don't have any palladium sponge lying around but I'l see what I can seal up in a straw for a lil demo.it was pomodoro who said he may or may not with-hold info at will in the beginning of this thread.
Sorry about the late reply but I just came back from the patent office. I'm winding up these hydrogen karpen cells but as promised will try out the Pt black vs Shiny Pt in air very soon. Will post results ad soon as I have them.
ok pomodoro let's see your plat-air results :D :D :D :D etch the bottom one please
Ok top one is etched and platenized Pt other one is etched Pt. Electrolyte is 1M NaOH. Left them shorted 24 hrs and I let them charge up overnight.
I'm going to put both up on top near each other and see if a potential difference still develops.
If you got no impurities in your plating process then both submerged will drop in voltage.both at top will also drop in voltage.you can even use 2 identical black foils for this test or two identical smooth foils and get same result.two platinum wires cut from the same piece will also give same result.raise your top one higher for more voltage
Blackened or smooth nickel foils,wire,ribbon will also give same results
OK guys, I'm officially giving up on the hydrogen karpens. Im definite that they don't work as I have performed them. The cathode always end up equilibrating to the same potential as the palladium after extensive discharging and does not recover. The early success was due to impure hydrogen, containing small amounts of oxygen. Since we are looking at microampers, this oxygen keeps powering the cell. Now I know that you, Profitis , think that I, thanks to you, have discovered something amazing and am keeping it from you, but no, that is not true. It is up to you to invest in some foolproof equipment with larger electrodes and to find out the truth for yourself. Please stay away from straws and hair thin wires. I'm thankful to you for all the advice, you are a very smart chap with great ideas, so keep going and re do these experiments for yourself. But for the other readers I really must say what I believe is true, and that is simply that these experiments, done in the way I did, show that a potential between the dissimilar metals doesn't last in a pure hydrogen atmosphere.
Please, anyone who wants to try these for themselves, do them properly, there must be no oxygen at all, or all you are doing is 'burning' up the hydrogen on the platinum.
Nuf said.
Having said that, if the platinum electrodes show a constant differential in air, then I might investigate those further, but no more hydrogen, please.
Pomodoro, thanks again for all the time, money, and quality effort that you put into these experiments.
Thanks markE you're very welcome.
Exellent pomodoro.although I only agree with 50% of your hydrogen results its been great many thanks.I've myself learned a good thing or 2 from this manhatten test series as have you I'm sure.let's see what your o2 results have to say.
Etched nickel mesh submerged in Na2CO3 sol with blackened nickel mesh ontop.oxygen spillover in action.this will not work under argon or nitrogen gas.you can make these electrodes as stinking big as u want.break the micrometer if u wish.
This snapshot at the height of the powerburst curve.this type of spillover entirely spontaneously reversable.
Double-step spillover from nickel black onto etched onto etched in rapid succession(everything submerged this time).note the negative potential at the end indicating definite o2 spillover and not galvanic corrosion(wouldve been positive or zero).this will not work under argon or nitrogen.
Well guys I need a break from this research, so this Will be my last post for now. The Pt black vs etched Pt did have a small voltage develop when they were placed in a solution of ammonium chloride. I measured 22 mv , but after 4 days it has died town to 9. This is after being shorted for a few days.
Keep the work going profitis , and good luck. For now I'm going to get my hands dirty with RF. I have a working 2kw cw 27mhz oscillator that I'd like to put to some use. I need to brush up on Stiffler , Avramenko, and moray as I have not been keeping up for 6 years or so.
Chloride ion (cl-) visciously corrodes platinum in presence of air pomodoro hence your evening out of potentials using nh4cl which is why I recomended (nh4)2so4 or NaOH thanks anyway.goodluck with the stiffler thingy
Pomodoro, thanks again for all that you put into this.
Double stepdown o2 spillover in rapid succession in Na2CO3 sol from mno2/pt onto etched ni onto etched ni.the slamming negative potential at the end ruling out galvano-corrosi.
Double stepdown o2 spillover in rapid succession in Na2CO3 sol from pt/mno2 onto ni(oh)2/carbon onto ni etch.slamming negative potential at end ruling out galvani-corrosi.
And a final fuck for the case of o2 spillover.pt wire vs mno2 ontop pt foil.please note: the standard potential of mno2 is less positive than the standard for pt in alkali yet here is reversed due to spillover gradient.pt wire was used as prongs on both clips in this shot.
From the international journal of modern chemistry.possibly the most important document I have ever seen that is official.I'm going to ask viewers to please not disturb the author.search for the word 'spillover' in here.verification that the second law of thermodynamics is no longer valid and being taken seriously
Do you think it is important that the author seems to represent that rusted iron is lower entropy state than unoxidized iron?
How does the "International Journal of Modern Chemistry" rank as a peer reviewed journal? How many articles in better known journals cite any articles in the IJMC? Does it rank up there with Andrea Rossi's JONP?
Rusting of iron: lower total entropy state than was previously thought taking into account phase-change of o2 gas disorder into orderly crystalline Fe2O3 oxide solid.ruthenium dioxide:total spontaneous reduction of entropy state taking into account phase-change disorderly o2 gas into orderly crystalline chemisorbed state.which journal would you prefer @mark E.mr chang has plenty articles in plenty journals.
Quote from: profitis on September 21, 2014, 10:05:53 AM
Rusting of iron: lower total entropy state than was previously thought taking into account phase-change of o2 gas disorder into orderly crystalline Fe2O3 oxide solid.ruthenium dioxide:total spontaneous reduction of entropy state taking into account phase-change disorderly o2 gas into orderly crystalline chemisorbed state.which journal would you prefer @mark E.mr chang has plenty articles in plenty journals.
The paper such as it was, addressed processes tat supposedly result in spontaneous reductions of entropy due to catalysts. Admitting that a claimed example does not result in the reduced entropy claimed, admits the paper fails to make its case.
If you had put your glasses on you wouldve seen that he claims LESS entropy for RUSTING not negative entropy for RUSTING.same applies to any oxidation corrosion process involving gases eg zinc + o2 = zinc oxide + energy ,,minus energy it took to suck o2 gas disorder into orderly ZnO crystal.same for sodium peroxide,calcium oxide,hydrogen ox..(oops)
Suggesting that people before him have made a miscalculation that overstates entropy is a complete fail in terms of offering support for the paper's stated claim of evidencing processes that spontaneously reduce entropy.
Get your calculator out: for a zinc-air bat as prime example,,2Zn + O2 = 2ZnO + energy - phase change energy.2ZnO + energy - phase change energy = 2Zn + O2 + phase change energy.you gain on phase change energy.unless you can show better math
Quote from: profitis on September 22, 2014, 05:28:51 AM
Get your calculator out: for a zinc-air bat as prime example,,2Zn + O2 = 2ZnO + energy - phase change energy.2ZnO + energy - phase change energy = 2Zn + O2 + phase change energy.you gain on phase change energy.unless you can show better math
Taking energy out of a battery, Zn-air qualifies, always results in an increase in entropy.
Not in a battery where your phase-change gain exceeds irreversability losses no.also not in a battery where both your electrode reactions are the same but opposite direction as is the case for catalytic spillover.
Sheehans paper along same line as chang et al http://meetings.aps.org/meeting/mar14/session/a2.11
Quote from: profitis on September 22, 2014, 11:39:03 AM
Not in a battery where your phase-change gain exceeds irreversability losses no.also not in a battery where both your electrode reactions are the same but opposite direction as is the case for catalytic spillover.
You keep saying that you know of battery chemistries that violate the second law. But when it comes to actually establishing that is true for any case you offer little more than hand waving. Pomodoro went to a great deal of trouble to entertain your ideas and the results were negative.
Quote from: profitis on September 22, 2014, 12:30:14 PM
Sheehans paper along same line as chang et al http://meetings.aps.org/meeting/mar14/session/a2.11
Bad link.
We cannot rely on pomodoro.he explicitly stated that he may or may not with-hold info at will therefore you have to look at results here through the spectacles of a highly trained electrochemist to see anything suspiciously worthwhile here.in other words pomodoro may or may not have served his own interests from given information.pomodoro may also have been hesitant to show something here even if he wanted to its a coin toss what you make of these results.I can assure you however that catalytic spillover is a very very textbook phenomena wether it be hydrogen or oxygen variety.it is in my laboratory-power to show oxygen spillover variety eg the nickel-mnO2 variety without a shred of doubt behave in reversable manner.the negative potential shown in the step-down spillover tests absolutely rule out any kind of galvanic corrosion.you will get this distinct mark only in a spillover cell,any spillover cell.this marker-potential will always be positive for the hydrogen moiety and negative for oxygen moiety.this distinct signal is absent from corrosion-dominated species
Let me see if I can get the sheehan link sorted.
Quote from: profitis on September 22, 2014, 03:48:51 PM
We cannot rely on pomodoro.he explicitly stated that he may or may not with-hold info at will therefore you have to look at results here through the spectacles of a highly trained electrochemist to see anything suspiciously worthwhile here.in other words pomodoro may or may not have served his own interests from given information.pomodoro may also have been hesitant to show something here even if he wanted to its a coin toss what you make of these results.I can assure you however that catalytic spillover is a very very textbook phenomena wether it be hydrogen or oxygen variety.it is in my laboratory-power to show oxygen spillover variety eg the nickel-mnO2 variety without a shred of doubt behave in reversable manner.the negative potential shown in the step-down spillover tests absolutely rule out any kind of galvanic corrosion.you will get this distinct mark only in a spillover cell,any spillover cell.this marker-potential will always be positive for the hydrogen moiety and negative for oxygen moiety.this distinct signal is absent from corrosion-dominated species
WRT Pomodoro, that's one speculation piled on top of another.
Assure all you want. We know that these text books do not claim violations of the Second Law, as you keep representing they tacitly do. So it would seem that their authors interpret the contents much differently than you do.
Google 'sheehan epicatalysis' for that paper. I never claimed that textbook authors on spillover point out a kelvin discrepency.spillover researchers are paid to research industrial catalysis and improve industrial catalysis and nothing more.the fact remains that the original karpen cell itself and all catalyst cells like it indeed behave in a manner consistent with textbooks ie.they behave in a manner consistent with catalytic spillover.a handfull of guys have now noticed its horrifying reversability.
Quote from: profitis on September 22, 2014, 05:26:47 PM
Google 'sheehan epicatalysis' for that paper. I never claimed that textbook authors on spillover point out a kelvin discrepency.spillover researchers are paid to research industrial catalysis and improve industrial catalysis and nothing more.the fact remains that the original karpen cell itself and all catalyst cells like it indeed behave in a manner consistent with textbooks ie.they behave in a manner consistent with catalytic spillover.a handfull of guys have now noticed its horrifying reversability.
OK, so you can't fix the link. Let's set that aside.
Your statement that:
QuoteI never claimed that textbook authors on spillover point out a kelvin discrepency.
appears to undermine months and months of representations by you that text books support your Second Law violation claims. You've just given Sarkeizen a field day.
If you come up with actual evidence to support your ideas then I will look. I have little interest in hunting down references that you say support your ideas when you cannot even seem to locate those references. It kind of boggles my mind how you can feel certain of the contents of something that you do not have available to review.
Very simple.you take catalysts that are impossible to galvanicly corrode eg nickel-hydroxide,Fe2O3 or TiO2 or MnO2 or FTO and see if you get a spillover-marker potential btween them.(And you do).you also take metallic galvanic couples that give a spontaneous-reverse potential eg Au-MnO2 or impossible galvanic potential eg Pt-Pt, Ni-Ni,TiO2-TiO2 and check for the marker-potential.comparison under nitrogen or argon helps too
Quote from: profitis on September 23, 2014, 02:14:25 AM
Very simple.you take catalysts that are impossible to galvanicly corrode eg nickel-hydroxide,Fe2O3 or TiO2 or MnO2 or FTO and see if you get a spillover-marker potential btween them.(And you do).you also take metallic galvanic couples that give a spontaneous-reverse potential eg Au-MnO2 or impossible galvanic potential eg Pt-Pt, Ni-Ni,TiO2-TiO2 and check for the marker-potential.comparison under nitrogen or argon helps too
These are your claims, so you are free to arrange whatever experiments you feel will support those claims.
These are not my claims.these are the textbook claims.according to the textbook literature, spillover should happen between eg. MnO2 and nickel-hydroxide.you are free to test a profitis cell to your hearts content.it is capable of many times original karpen power density in a multi-cell battery.
I can propose an experiment. Have Profitis come up with a list of how a rate change
in the the spillover reaction would manifest itself in several different cells. Then expose
those cells to a step increase in a PEP-II neutrino beam at the Fermi-Lab accelerator's
2MW PEP-II neutrino beam. So that the cell receives from 2 to 10 times the standard
flux of neutrinos. As a show stopper also vary the neutrino mass through a range
and show that there is a resonance like tuning peak in the spillover reaction exactly
at the PEP-II neutrino mass.
:S:MarkSCoffman
One step at a time markscoffman.with a maxwell demon catalyst sending the redox reaction to the left at one electrode and to the right at the other,there is no need for anything except ambient temperature.
O2|Ni|[OH-][(Fe(CN)6)4-]MnO2|O2
H2|C|(H+)(Cl-)|Ag