Plasma electrolysis at lower voltages

  • Alan Smith

    Indeed, thick formations of apparently decomposing hot potassium carbonate would form around the cathode. Sometimes they would detach from it and burst at a distance, or deflate with the emission of hot particles. I imagine that the potassium vapor formed as suggested in the PDF you linked would rather quickly form KOH.



    I found interesting that heating of some sort was still going on and sufficient to cause K2CO3 to heat up that much in relatively large amounts.

  • Alan Smith

    Since the solution is saturated, the pH should be already rather high and possibly the small amount of KOH added this way might not influence it too much. I don't have suitable means at the moment for measuring this, though.




    Speaking again of cathodic plasma electrolysis at lower voltages than usual, in a paper (attached here, from page 79+) Takaaki Matsumoto described the usage of K2CO3 as electrolyte at 1.5M concentration. He came up with this current-voltage diagram (annotations mine):



    Although his experiments have already been performed at lower voltages than other researchers, in my case with the saturated hot K2CO3 solution, Vd appeared to be significantly lower than his ~85V (but accurate measurements were difficult due to potassium carbonate blocking the cathode).



    One interesting thing mentioned in the paper, though, is:


    Quote

    Fig. 4 shows a sequence of pictures for the tiny sparks, in which they were accidentally separated from the surface of the palladium cathode by two explosions. The first small explosion took place in the gas atmosphere over the water level, which was triggered by the tiny sparks, as shown in Fig. 4(a). Due to mechanical shock from the explosion, a group of the tiny sparks were separated from the cathode, and were driven by the electrical potential towards the anode, as is shown in Fig. 4(b). The tiny sparks were decayed on the anode to trigger the second explosion, as shown in Fig.4(c). These pictures showed that the tiny sparks were negatively charged and could exist in water solution as independent bodies.


    I have never observed these in all the testing made so far, except for today once I used concentrated enough K2CO3 solution to produce deposits on the cathode that would glow and to some extent explode. I wonder if a form of this is what Matsumoto observed, since apparently during glow plasma electrolysis the electrolyte tends to concentrate close (and on) to the cathode, while this does not happen during normal electrolysis in the same electrolyte.

  • It might be common knowledge, but I wasn't fully aware of this during the tests performed. It looks like the boiling point of highly concentrated aqueous hydroxide solutions like KOH is greatly increased relatively to that of plain water. Graph for KOH:



    Source: digitized and converted to Celsius from https://www.oxy.com/OurBusines…/KOH-Handbook-2018-ed.pdf


    For NaOH:



    Source: http://www.cheresources.com/in…_database/oxy_caustic.pdf


    And K2CO3 (this, I did notice after measuring 116 °C from the saturated solution I tested recently):



    Source: digitized from https://www.armandproducts.com…nt/pdfs/k2so3Complete.pdf

  • In order to extend the usable voltage range of my adjustable power supply I recently got a 36V 10A fixed voltage DC PSU. Surprisingly, not only it is adjustable in a relatively wide 26–41V range, but it also has floating outputs, which makes it more flexible than laptop/computer PSUs which are usually ground-referenced (I checked the ground connection and it was ok).



    Not much difference in reaction at higher voltages at least up to the maximum I could reach overall (72V), although the plasma starts to acquire a more violet hue reminiscent of potassium there. Cathode wear and reaction intensity (noise, etc) also start becoming significant and for practical purposes it might not be useful to go much higher since then the experiments would only last minutes.


    The applied current only increases after the minimum abruptly reached at about 31–35V (under hot K2CO3 electrolyte conditions at high concentrations depending on temperature; when cold this threshold is higher) and in one test I could plot a similar voltage-current curve:



    The highly dynamic conditions make it difficult to plot an accurate graph in this respect, since the reaction changes quickly with electrolyte temperature and concentration, and both change during operation given the relatively small amount of electrolyte solution used.




    Perhaps the most significant observation so far is that at the high electrolyte concentrations used, at the same voltages where plasma electrolysis occurs, the K2CO3 electrolyte appears to slowly accumulate on the surface of the cathode in relatively large amounts. Local temperature can occasionally even reach levels high enough to turn it incandescent and melt it, sometimes bursting with the emission of potassium-like light as shown previously. Possibly, electrolytic decomposition of the solid electrolyte to metal also occurs to some extent, while water electrolysis still continues.


    It would seem that this accumulation process is somewhat related to the plasma electrolysis phenomenon, i.e. that plasma electrolysis could be occurring because (or also because) of the strong increase in electrolyte concentration close to the cathode (K+ ions in solution, here). Since increasing the concentration of the electrolyte in the solution very easily lowers the voltage from which the electrolytic plasma process starts also (beyond conductivity), at least on an intuitive level this seems correct.



    Whether allowing the electrolyte to accumulate like this is advantageous, I'm not entirely sure. The cathodic plasma appears to be still occurring to some extent below the surface and on the exposed cathode portion, but not as with the clear surface.


    On their own, conditions where hydrogen atoms (from electrolysis) are forced through alkali as partially molten salts and as metals could be interesting, though. LENR in molten salts has indeed been reported in the past, although under different conditions than what I've tested so far. Just a couple examples from lenr-canr.org:

  • I have always used the type of PSU you picture above. Pretty stable and reliable. The current workhorse however is different- a 60V 40A server PSU. They sometimes turn up on ebay, which is where I got 2 new ones for around $100 delivered.

  • I haven't tested it long and deeply enough to verify how reliable it is, but it seems well-built. The floating outputs also make it more suitable for laboratory usage.


    I set it to 31V so that after arranging it in series with my bench power supply (0–31V selectable) I can more or less seamlessly adjust voltage in the 0–62V range.

  • It turns out that Randell Mills also has worked (at least for a period) on plasma electrolysis and been suggesting that hydrinos are produced in these systems. In some of the published patent applications there are descriptions of plasma electrolysis devices, like for instance in the abandoned US20040247522A1 - Hydrogen power, plasma, and reactor for lasing, and power conversion. Below is a composite image with relevant excerpts and figure extracted from it.



    Interestingly, the use of vibrations for the cathode and/or the solution is suggested. I also thought of something along these lines (but haven't applied it yet); I think it could help forming a gaseous layer around the cathode and start plasma electrolysis at lower voltages in particular when the electrolyte solution is cold.


    But more than this, of more interest is the possibility of using more than one electrolyte, in particular the "catalysts" reportedly useful for producing hydrinos. This would mean for instance having not just K2CO3 (or KOH) but also other compounds-catalysts in solution at the same time, as this could plausibly help lowering the voltage from which the process starts. A lowering of the voltage of plasma generation under the presence of these catalysts has already been reported by Mills with gas discharge cells in some publications.


    There's a paper from Mills et al. where plasma electrolysis has been used; I'm not sure if there is more on the same topic:



    Along these ideas, I tried adding sodium bicarbonate to the previously made concentrated K2CO3 solution, hoping it would decompose to sodium carbonate at the higher than water-boiling temperatures reached (115–120 °C), but [perhaps not too unexpectedly] it made things worse, with more severe blocking of the cathode by electrolyte accumulation. I'm not entirely sure if this was because of the bicarbonate and conversion of potassium to bicarbonate or because it would not have helped anyway to add anything more under the close-to-saturation concentration conditions.



    These electrolyte "sticks" are what I kept frequently removing from the thin tungsten cathode. Sometimes, when crushed just after/during removal they produced sparks and emitted tiny but dense smoke plumes; I think elemental Na-K is formed under these electrolyte accumulation conditions due to the electrolyte itself getting electrolytically decomposed.


    These formations prevent plasma electrolysis from taking place; a form of normal electrolysis at high current occurs instead with them. When the hot electrolyte solution concentration is high enough under their presence, sparks and explosions from larger electrolyte formations start occurring, as I showed previously. More spark-like features started appearing today after I added NaHCO3.


    This might work better using LiOH–NaOH–KOH and other soluble hydroxides of the elements listed as hydrino catalysts, but it needs more professional equipment and testing conditions than what I can provide. Furthermore, the solubility of mixtures of common electrolytes is likely to be different than that of the separate electrolytes, and that needs to be investigated.

  • A lot of the basic information you need can be found in this - now very old - 1902 - source book. The basic science remains pretty much unchanged, and it was written by Ahrennius, a master of the subject. I use it as a reference book for the basics and beyond. The physics and the methods might have changed in the last 120 years, but the behaviour of the materials remain the same.


    ofelectrochemistry handbook 1902..pdf

  • .

    Quote

    Sometimes such transition has been pointed out in related literature, but I don't recall where exactly

    It's also effect of Energoniva device. The purple color is sometimes attributed to Rydberg resonance transitions (compare the ball lightning phenomena which like negentropic artifact exhibits power spectrum of the opposite slope than the Planck body radiation.


    Quote

    It is not easy to find affordable regulated power supplies for these experiments

    Actually every welding inverter provides more than sufficient energy source for such a fun..


    Quote

    The solution turned completely opaque dark violet and not much could be seen of what was going on with the reaction except from hints at the surface

    This is a sign of interesting iron compound formation: potassium ferrate (analogous to violet permanganate of manganese metal)

  • Actually every welding inverter provides more than sufficient energy source for such a fun..

    In the opening post where I wrote that as an introduction, I was referring to high-voltage power supplies commonly used for plasma electrolysis experiments (technically also known as "contact glow discharge electrolysis" or "CGDE"). VARIACs are often used and I could have got one, but besides maybe a fuse, they don't have any built-in safety feature.


    In principle it should be possible to use a welding power supply for the experiments described here, but many low-end cheaper models such as the one you linked don't allow to directly vary voltage, or only allow to vary it on a limited range; not from 0V.


    Keep in mind that the reaction observed here is not an electric arc and unlike them, it does not need current limiting to be properly and safely driven. I don't need tens–hundreds of amps, only a few at most, and during the glow plasma discharge typically much less than 1.


    A lot of the basic information you need can be found in this - now very old - 1902 - source book. The basic science remains pretty much unchanged, and it was written by Ahrennius, a master of the subject. I use it as a reference book for the basics and beyond. The physics and the methods might have changed in the last 120 years, but the behaviour of the materials remain the same.


    ofelectrochemistry handbook 1902..pdf

    I definitely need a basic electrochemistry read, but to clarify one point here: the electrolyte mixture, under cold conditions, appears to be completely dissolved. It's only when voltage is increased to a level close to where plasma electrolysis starts that it accumulates close to the cathode and onto it in solid form.


    I'm aware that during electrolysis the electrolyte concentration locally varies, so it could be dynamically exceeding the solubility threshold under the conditions tested.

  • You may have stumbled into the inverted solubility zone - decreased solubility with increasing temperature. This is the case with potassium carbonate.


    The solubility of potassium carbonate in water at temperatures from 384 to 529 K is reported at the saturation vapor pressure of the solutions. Measurements were made using a visually-accessible apparatus consisting of a platinum cell with sapphire windows and gold seals. The results indicate that potassium carbonate remains prograde-soluble up to 529 K. At approximately 427 K the hydrate form of the solid changes as indicated by visual observation of the solid and a change in the solubility behavior. Solubilities determined at lower temperatures have been compared with literature data and are in good agreement.[


    https://www.researchgate.net/p…sing_the_Synthetic_Method



  • Alan Smith

    Here is relevant data from the indicated paper (I added Celsius scale on the right graph).



    From here it does not look that the solubility decreases above 427K, only that it increases slower. It could still be that at higher temperatures the solubility actually starts decreasing, though.


    It could also more simply be that the rapidly boiling water around the cathode causes precipitation and local accumulation of the electrolyte, and that conditions are such that the phenomenon became macroscopic.

  • Diluting the potassium carbonate–sodium bicarbonate (mostly decomposed to carbonate, I would think) solution for the most part mitigated the electrolyte accumulation issue, but the so-called mid-point voltage (voltage at which current is minimized) shifted above 50V, even at a temperature greater than 90 °C.



    Due to sodium ions, plasma color at the [still partially blocked, it seems] cathode even at 62V was intense yellow (see gif below). At the same time, slow-moving strings (?) could be seen moving upwards in its proximity, which I also observed in earlier tests.


  • Quote

    but many low-end cheaper models such as the one you linked don't allow to directly vary voltage, or only allow to vary it on a limited range; not from 0V.

    Not actual problem: the solution is highly conductive and these are soft voltage sources, i.e. initial voltage is so low, that it's not even sufficient for ignition of discharge: only electrolysis runs. I did experiment with LiOH and LiOD solutions with using them. No one is required to use welding inverters for experiments - I just opposed the claim, that suitable electric source is expensive and/or difficult to get.

  • Most IGBT welding machines have an open-circuit voltage ranging 55–75V, which on its own would seem sufficient for at least starting a glow discharge plasma in concentrated electrolyte solutions as described in this thread. How this is maintained under light load would be the main issue; controllability, a close second.


    There are several cheap options for getting a few hundred volts at a few amps, but regulated, safe-to-use power supplies of sufficient power for entry-level laboratory use tend to be expensive.


    The finding (probably not novel, but likely not widely known) that at a sufficiently high electrolyte concentration the same processes can be observed in the 30–60V range means in any case that widely available and affordable bench power supplies can be used instead, without need for high voltages—this was my initial point.

  • I found this graph for Na2CO3 which easily explains why the problem became more severe with it (assuming complete decomposition of NaHCO3 with time and temperature).



    Found here, but actual source unknown: https://www.quora.com/Na2CO3-+…-this-equation-reversable


    [...] More spark-like features started appearing today after I added NaHCO3.

    I made a short video of that. They appear under certain conditions when the electrolyte starts accumulating on the cathode and presumably electrolytic dissociation into alkali metal starts occurring:


  • Hei Can! I don't know what your experiments are aimed at (e.g. excess heat, transmutation, radiation, etc.), but I can tell you that you can obtain an electrolytic plasma even at lower voltages and lower currents compared to the ones you are using. I made this kind of experiments many years ago, following some suggestion from another researcher. There are two key factors to obtain a wide range of unusual phenomena: large availability of H+ ions and current density in the cathodic zone. In other words, you should use very low pH (very acid) solutions, large anodes and very small cathodes (e.g. a thin wire or even a "point"). Also, in order to increase the cell conductance, it has to be "thin", not "flat": I mean more like a test tube than a beaker.

    Years ago I used a solution of HCl only (about 10%) in a small vial, a Ni chip as the anode and a 0.5 mm diameter Fe wire. The power was from a 12 V Li-ion cell (3S). The original idea was that Ni would be dissolved from the anode and goes into solution as Ni++ (it is just like having a NiCl2 solution) and then would be plated on the cathod together with lot of H+, so to obtain a very higly loaded material. This would actually happen if you limit the current to 10s of mA, but without limting it, you can get plasma and a black denditic deposit on the cathod. In order to get plasma, you have to insert the cathod wire slowly from above the liquid surface. The plasma will ignite and can be maintained to some extent. Apparently current is not very high (100s mA), but the solution become very hot immediately. I've been told that if you place a magnet close to the cell, you can record some counts with a Geiger counter (never tryed).

    BTW, a couple of days ago I made a similar experiment, and I used a webcam with the Cosmic Ray Finder software in order to detect something anomalous. It recorded 3 events while the current was limited to few tens of mA, than when I increased it to 1 A for about 1 second, the webcam stopped working completely (it was permanently damaged)... :/

  • Stevenson

    I am mostly looking at what parameters appear to lower the voltage from which the cathodic glow discharge plasma starts under alkaline conditions. I made a new thread to separate these efforts from previous ones using a low-current high-voltage power supply.


    Using KOH, results seem to be proportional on electrolyte concentration, also beyond the point from which maximum conductance would be achieved.


    Best results with concentrated KOH solution seem about 12V for breakdown (voltage above which current starts decreasing rapidly and possibly sparks be observed in the dark) and 28–29V for a clearly visible plasma, but results (especially for the breakdown voltage) vary significantly depending on temperature and wire type and geometry. A run had a similar voltage-current relationship, but it was with a 0.3 mm worn tungsten wire immersed for just a couple mm in the electrolyte:



    Small-diameter (in the order of 0.3 mm or less when they wear up) resistive wires that do not oxidize easily (like Ni) work well, but since they tend to melt easily tungsten tends to be the most practical choice. Cu melts too easily; Ti burns easily. A greater immersion depth also may also remove more heat from the wire and make the reaction worse.


    Years ago I used a solution of HCl only (about 10%) in a small vial, a Ni chip as the anode and a 0.5 mm diameter Fe wire. The power was from a 12 V Li-ion cell (3S). The original idea was that Ni would be dissolved from the anode and goes into solution as Ni++ (it is just like having a NiCl2 solution) and then would be plated on the cathod together with lot of H+, so to obtain a very higly loaded material. This would actually happen if you limit the current to 10s of mA, but without limting it, you can get plasma and a black denditic deposit on the cathod. In order to get plasma, you have to insert the cathod wire slowly from above the liquid surface. The plasma will ignite and can be maintained to some extent. Apparently current is not very high (100s mA), but the solution become very hot immediately. I've been told that if you place a magnet close to the cell, you can record some counts with a Geiger counter (never tryed).


    In the past I attempted something loosely similar at low voltages (fixed 12V) using 10% HCl solution with closely-spaced electrodes (but not thin). I observed sparking, but with a different working mechanism than a glow discharge as in these experiments. As I saw it, the anode (steel) would rapidly dissolve in the strongly acidic solution, deposit material on the cathode and eventually form a short-circuiting "bridge" with the cathode due to the small electrode spacing. The bridge would then vaporize and the cycle would repeat many times.


    The main issues were unreliability (often the short-circuit would not be able vaporize the deposition bridge formed, so the electrodes needed to be manually separated often), and the amount of chlorine evolved from the reaction which made it unsuitable for prolonged operation, especially without a suitable testing environment.


    EDIT: the above process wasn't much related to what you suggested, please ignore (I left these paragraphs here anyway, just in case).


    BTW, a couple of days ago I made a similar experiment, and I used a webcam with the Cosmic Ray Finder software in order to detect something anomalous. It recorded 3 events while the current was limited to few tens of mA, than when I increased it to 1 A for about 1 second, the webcam stopped working completely (it was permanently damaged)... :/


    I am also using the Cosmic Ray Finder application with a slightly modified cheap webcam (lens removed, Al foil in front of the CMOS sensor), no lead shielding and lowered detection threshold (since it is not necessarily muons or cosmic rays that have to be detected).


    Results with it so far do not suggest that much is going on besides background activity (about 250 detection events/day on average at the current settings). As it is, it appears to be working like an insensitive Geiger detector, since it responds to weak gamma sources (KOH/K2CO3 canister) and lead shielding similarly to the detector I previously had.

  • Years ago I used a solution of HCl only (about 10%) in a small vial, a Ni chip as the anode and a 0.5 mm diameter Fe wire. The power was from a 12 V Li-ion cell (3S). The original idea was that Ni would be dissolved from the anode and goes into solution as Ni++ (it is just like having a NiCl2 solution) and then would be plated on the cathod together with lot of H+, so to obtain a very higly loaded material. This would actually happen if you limit the current to 10s of mA, but without limting it, you can get plasma and a black denditic deposit on the cathod. In order to get plasma, you have to insert the cathod wire slowly from above the liquid surface. The plasma will ignite and can be maintained to some extent. Apparently current is not very high (100s mA), but the solution become very hot immediately. I've been told that if you place a magnet close to the cell, you can record some counts with a Geiger counter (never tryed).


    Just tried again properly with 10% HCl, worn tungsten wire cathode, but steel anode. Indeed, in this non-optimal setup it appears that a visible [blue-colored] plasma can be observed even at 18–19V or so, but only if the cathode is very sharp and barely immersed in the electrolyte. If dendritic deposition occurs the surface area increases and the voltage from which the plasma starts is too increased.


    I tried adding a magnet (position not optimal), and it has a beneficial effect in that it tends to pull away the particles (composed of iron, thus ferromagnetic) deposited on the cathode, keeping the voltage from which the plasma is observed low.


    Increasing voltage further makes makes the sharp cathode tip apparently glow from incandescence.


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    The amount of chlorine actually evolved is not significant, but chronic exposure to acidic fumes is harmful in nasty ways.




    EDIT: I suspect that the difficulties in maintaining the reaction are mainly matter of anode surface area. I did not want to use too much HCl so the immersed surface area ended up being limited. I tried again using several centimeters of Ni wire as the anode and it became more difficult to have a plasma along the same amount of surface area, although the minimum voltage from which it could be seen did not seem to be affected much.