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Initially the direction of plasma electrolysis was considered as the division of classical electrochemistry

1

Initially the direction of plasma electrolysis was considered as the division of classical electrochemistry, augmented by hypothesis about the contribution to the initiation of the chemical reactions of radiation of discharge, and it is later - the radiation chemistry effects, caused by the bombardment of the surface of solution with the generatable in the plasma ions. With “classical” electrolysis of the aqueous solutions of electrolytes the isolation of the basic gaseous products of oxygen and hydrogen is connected with the electrode reactions of discharging the ions of hydroxyl and hydronium. If the plasma contacts with the solution comes out as such electrodes, the situation changes. It is observed the isolation of detonating gas, that was not described by Faraday law. The current output of oxygen and hydrogen, which were being observed in the glow and contact discharges with all conditions considerably exceeds. Electrolytic processes have long ago been known and widely they are used in the chemical industry. 

Plasma electrolytic processes are revealed comparatively recently; therefore thus far there exists neither physical nor chemical of the theories of these processes. Preliminary analysis shows that the complete description of plasma electrolytic process cannot be based on purely physical or purely chemical ideas. These are - the interconnected physical chemistry processes; therefore to divide them into the physical and the chemical is possible only conditionally.

  

 

.

 

.

 

Steady obtaining of plasma is achieved at the different area of positive and negative electrodes. With sinking of pivotal electrode with the diameter of 4mm. in the electrolyte it is more than to 10mm. and to application of voltage from 0 to 250- TI of volts plasma does not catch fire. The gas generation increases on the electrodes with an increase in the stress and current grows. In the case, when strezhnevoy electrode is lowered to 3-4mm of lower than the meniscus, then with the electrode voltage of 60-70 volts begin spark breakdowns in the region of the gas generation of hydrogen. Smoothly increasing stress, characteristic rumble grows, spark breakdowns pass into the stationary combustion of plasma. Exceeding stress more than 150 volts leads first to melting of tungsten pivotal electrode, and then to its start of boiling. The concentration of electrolyte and temperature it is necessary to change in the dependence on the parameters of cell. A basic study was conducted in the alkaline electrolyte.  An increase in the stress leads to a change of the current strength in the chain, whose characteristic laws governing are shown in the given graph.  

    At first, with an increase in the stress it is linear, in accordance with Ohm's law, the current strength grows. Then, with the stress of more than 40 volts Ohm's law is disrupted, and (it is point 5) current strength decreases spasmodically with the stress of approximately 100 volts, and in cathode bright glow appears (plasma). Further forced decrease of stress (point 6- 15) insignificantly changes current strength. The glow in cathode disappears with the stress of approximately 60 volts (point 14 - 15); current strength spasmodically increases almost to the previous value. Glow in the electrolyte of na2SO3 - orange. With the melting of electrode and smaller contact area of plasma with the electrolyte, the glow passes into the violet colored. At this time current drain decreases several times. The radiation-monitoring measurement of emission was carried out by everyday radiation monitor Jupiter SIN-05 in the flow 30 min. with the removal of indications in 1 min. before the switching on of installation and afterward. Radiation monitor was located at a distance 10sm from the cell. Results are brought to the stated below table.  

минута

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

Естественный фон в лаборатории

 

0,14

0,15

0,17

0,11

0,23

0,12

0,18

0,19

0,12

0,21

0,19

0,20

0,14

0,13

0,16

0,21

Фон при горении плазмы

 

0,07

0,09

0,15

0,16

0,16

0,18

0,16

0,12

0,15

0,15

0,10

0,13

0,14

0,11

0,16

0,17

 

 

минута

17

18

19

20

21

22

23

24

25

26

27

28

29

30

общ.

Естественный фон в лаборатории

 

0,21

0,19

0,20

0,21

0,18

0,10

0,13

0,18

0,14

0,22

0,14

0,19

0,15

0,10

499

Фон при горении плазмы

 

0,11

0,18

0,11

0,12

0,09

0,15

0,12

0,19

0,10

0,15

0,15

0,17

0,13

0,12

409

 

 As you can see in the table,the burning of plasma is followed by decrease in a natural radiation background  about a cell. The theoretical explanation and conclusions of this phenomenon still should be drawn. First of all we were interested in the abnormal exit of hydrogen developed at plasma electrolysis, predicted by professor Kanarev F.M. As he notes in the work, perhaps abnormal thermal emission and release of hydrogen exceeding an exit on current by 10 times on some operating modes. There should be also found these "some modes". Having studied behavior of plasma and gas emission in the small closed volume, the laboratory reactor was manufactured of quartz glass of the bigger size with compulsory circulation of electrolyte. Power supply of the reactor was carried out by alternating current of industrial frequency - 220 volts. As the bigger on the area electrode, there was the metal gauze with a small cell.  At electrolyte circulation melting of the central tungsten electrode wasn't observed. After forty minutes of work in such mode the central electrode underwent an erosion and electrolyte got a brown shade. After upholding the settled powder had "rusty" color. It follows from this that direct connection of the reactor to the power supply network is inadmissible in the long mode. Comparative measurements of the thermal emission carried out in two open identical aquariums. In one there was an ohmic heating of electrolyte, in oth



er having heated due to plasma electrolysis. Electric energy was measured by the household electric meter (because of nonlinearity of consumption of current) by quantity of turns. Reference temperature of electrolyte -25°C. Volume – 9 Liter. Concentration of  Na2CO3 - 35g/l. Current variable - 220 volt. After inclusion of power supply, they reckoned electric meter turns. In that and other case the quantity of the consumed electric power was identical (480 turns). Temperature in an aquarium where plasma burned, was 9 °C higher, than in an aquarium where there was an ohmic heating. It is also necessary to consider that in the course of heating in environment the "plasma" aquarium had a thermolysis - 21min, and the second - 11min. Thedifference in the thermal emission increases ifexperience to begin above 65 °C with electrolyte temperature. At this stage all parameters (an alternating, direct current, concentration of electrolyte and its structure, optimum tension, etc.) weren't investigated at which electrolyte heating by plasma as much as possible in comparison with ohmic heating. Having inspired by the first progress of abnormal allocation of heat, especially without energy of the emitted hydrogen, we passed to quantitative measurements of release of gases.There was made the electrolytic installation with a water lock for collecting the allocated gases. The bottom of an electrolytic cell from metal served as the flat anode. In a cover there was made the opening for the tungsten rod cathode in a porcelain tube.

 

 At inclusion of power supply plasma lights up, there is a release of gases. In a water lock emergence of bubbles is visible, but their quantity intuitively doesn't correspond to the consumed current. As there was a tightness of the top cover not is capable to detain hydrogen because of its strong penetration. Other option of an electrolytic cell was chosen. The turned glass capacity filled with electrolyte was located on arms in an aquarium. From below the isolated electrode was brought (-). The flat electrode (+) from stainless steel, was aside. Allocation in plasma of hydrogen and vapors of water forced out electrolyte from glass measured capacity. After condensation of vapors and cooling of capacity to room temperature volume measurement of the emitted hydrogen was carried out. On some operating modes the sound radiation of plasma led to emergence of the Big Cavitational Bubble (BCB) described in the work of Margulies  M. A. "Sound chemical reactions and sonolyuminestsention". Its movement in volume had chaotic character. Influence (BCB) on stimulation of release of hydrogen wasn't investigated.

At inclusion of power supply plasma lights up, there is a release of gases. In a water lock emergence of bubbles is visible, but their quantity intuitively doesn't correspond to the consumed current. As there was a tightness of the top cover not is capable to detain hydrogen because of its strong penetration. Other option of an electrolytic cell was chosen. The turned glass capacity filled with electrolyte was located on arms in an aquarium. From below the isolated electrode was brought (-). The flat electrode (+) from stainless steel, was aside. Allocation in plasma of hydrogen and vapors of water forced out electrolyte from glass measured capacity. After condensation of vapors and cooling of capacity to room temperature volume measurement of the emitted hydrogen was carried out. On some operating modes the sound radiation of plasma led to emergence of the Big Cavitational Bubble (BCB) described in the work of Margulies  M. A. "Sound chemical reactions and sonolyuminestsention". Its movement in volume had chaotic character. Influence (BCB) on stimulation of release of hydrogen 

 

wasn't investigated.

Under the first law of Faraday, the quantity (in our case volume) the allocated substance is proportional to current and time of its passing through solution. Comparative experiences of release of hydrogen at plasma and usual electrolysis showed that violation of the law of Faraday takes place. In our experiment on plasma electrolysis, hydrogen it was allocated 2/3 more. In acid H2SO4 electrolyte this indicator is even higher, than in the alkaline. Influence of concentration and temperature of electrolyte on release of hydrogen at plasma electrolysis is thoroughly not investigated. Considering the abnormal thermal emission of plasma, plus energy which contains the allocated hydrogen, we found it possible to make installation in which energy of combustion of hydrogen will go for heating of electrolyte and as a result creation of the economic heat generator. Collecting in one capacity of oxygen and hydrogen in a large number it is dangerous for a cause of explosion. Therefore we placed electrodes (one rod and ring electrode on one holder) closer to the top part of thick-walled glass capacity in a such way, so that the volume  was approximately 300ml. 

Inclusion of installation is followed by emergence of plasma and intensive lowering of the level of electrolyte in a flask. In case in a flask there is only one electrode, (-) that hydrogen, forcing out electrolyte and "having touched" plasmas, extinguishes it and electrolysis process stops. When detonating gas gathers under a flask, at achievement of a gas layer of plasma there is an insignificant explosion, and level rises in initial situation. The cycle is repeated. Thermal energy of compound of oxygen and hydrogen thus doesn't dissipate, and goes for heating of a surface of a flask and electrolyte. If to place all surface of a flask in an aquarium, energy of plasma, ohmic and recombinational compound of hydrogen and oxygen, will be given to all volume of electrolyte.

 

 

 For verification of this assumption and to measurement of a thermolysis of all installation we shipped a reactionary flask lower than a level of electrolyte in an aquarium. Measurement of a thermal emission in this experiment is connected with certain difficulties. It is connected by that the recombination of detonating gas in volume of a flask depends on temperature of its walls. At a temperature about 100 °C the recombination passes "softly". In case the flask is lowered in electrolyte of room temperature, the recombination of hydrogen and oxygen occurs more brizantno. Especially it is shown in acid electrolyte.

 

 

 

  

 

Experiments with alkaline electrolyte showed that in certain cases combustion of detonating gas happens without strong explosion if intensive foaming takes place. Also we observed interesting cases of emergence of tongues of flame of red color in a flask which existed 3-4 sec. Thus cotton, explosion, didn't occur, and the level of electrolyte rose by former level.

Regularity of emergence of tongues of flame didn't manage to be found out. Numerous experiments to achieve "soft" combustion in all cases, didn't lead to identification of conditions under which there is a flame. Attempts after all to find a way of "not explosive" burning of hydrogen led us to success. Change of a configuration and arrangement of electrodes allowed to find a new type of plasma electrolysis. In this type of electrolysis almost completely there is no erosion of electrodes that is big advantage. For detailed studying of this type of electrolysis we made a special aquarium with the reported volumes. Externally work looks as follows. At inclusion of installation bright plasma with consumption of current peculiar to it lights up. Release of gases in working volume lower the electrolyte level until the category passes in new, found by us, a form of the ring category

  

Consumption of current upon transition sharply decreases approximately at 50-60 times. On the electrode, in the environment of detonating gas and vapors of water, it is necessary to burn a small flame in the form of a cone with the top turned up. Evaporation of vapors, release of hydrogen and oxygen visually lower level, at condensation and a recombination of detonating gas level rises. So-called "breath" with the period of 2-3 sec. and with an amplitude up to 6 mm is established. It reminds installation work, as in the electrolyzer mode, and a fuel element at the same time. In this option the excess repeated thermal emission since this type of the ring category at the established uniform "breath" consumes an electric power minimum is supposed. The consumed energy is so small that the disk of the household counter ceases to rotate if the top part of a flask (volume 500ml) is placed in air.

 

  


Temperature of the top part it is thin or a thick-walled flask, during experiment within 2 days, I remained a constant at the level of 100 °C, at the air temperature in laboratory of 22 °C. Any turn of a disk of the electric meter during this time didn't occur. Essential reduction of electrolyte in experiment it isn't revealed. The assembled revolving battery from 6 electrodes showed steady burning of a conical flame on each electrode. Thus the arrangement at one level is important! It is a way to accumulation of power at design of the heating unit. Limitation at that time, the control and measuring equipment didn't allow to reveal all characteristics and degree of an excess thermal emission of the ring category found by us. Accumulation in result of other researches of the equipment and experience we didn't come back to the detailed analysis of this type of the category.



 In order to reveal nature of excess energy release we continued studies of the processes of proceeding with the plasma electrolysis. It should be noted that contemporary concepts about cold synthesis affect the thus far only nuclear reactions, proceeding either in the crystalline substance (surface of electrode, target), or in the liquid (sonolyumenistsentsiya). Only separate theoretical works allow existence of the thus far unstudied state of the extremely no equilibrium plasma, in which is possible the flow of nuclear transformations at temperatures from 1000º of do3000ºC. Many works concern interaction of the hydrogen or deuterium plasma of the glow discharge with the material of cathode. In particular, Karabut A.B. (Russia) it presented the results of the experiments, in which with the bombardment of palladium cathode with deuterium ions with the energy of 0, 5-2keV, it registered the emission of photons (3MeV) and alpha particles (14MeV). Process was accompanied by X-radiation with the intensity to 100R/s and operating time of heavy nuclei with the speed of the order 1013s-1. On the assertion of the author the results of experiments are steady and can be easily reproduced. They are also of interest of work Japanese scientific T. Mizuno on the plasma electrolysis of ordinary water. In his experiments he used ordinary water with the addition 0, 05-0,2M  K2CO3, a tungsten cathode and a platinum mesh as the anode. The amount of heat, which is taken away from a cell, a stream of hydrogen and the brought power was fixed. In experiments there was steadily registered the abnormally big stream of hydrogen exceeding an exit on current to 20 times (fig. 9).  In some experiences process passed into an uncontrollable stage, and the glass flask in which experiment was made, explosed. In 20 seconds prior to explosion devices fixed the allocation of excess heat exceeding the brought energy just before explosion on three orders. Besides, after explosion on a surface of the tungsten cathode elements, earlier there the absent were registered. Material of which the electrode is made, has no basic value. For example, in his works Kanarev F. M. applied an electrode from iron. The content of chemical elements on a surface of nonworking cathode was following: 

 

 

                  Chemical composition of the cathode surface before work in solution:

 

       Элемент

     Fe

%

99,90

 

On a working surface of the cathode working in KOH solution there were new chemical elements.

 

Chemical composition of a surface of the cathode working in KOH solution:

 

           Элемент

     Si

     K

    Cr

     Fe

    Cu

%

0,94

4,50

1,90

92,00

0,45

 

The chemical composition of a surface of the cathode working in NaOH solution appeared another:

Элем.

Al

Si

Cl

K

Ca

Cr

Fe

Cu

   %

1,10

0,55

0,20

0,60

0,40

1,60

94,00

0,65

 

We investigated a working surface of an electrode on change of element structure. In our case the cathode was made of copper (99,9%). After short work in weak Na2CO3 electrolyte at a voltage of electrolysis of 200 volts, the electrode was handed over on the analysis.

Presence at a range of Ca, Si, Cl, K can be explained with impurity of these elements in the applied water. Traces of other metals, except electrode material, it was revealed not. The spectral analysis of the slime which settled owing to an erosion of an electrode showed existence of the synthesized elements which were absent at the beginning of experiment. The test for magnetic fraction showed existence of magnetic particles that testifies to synthesis of ferromagnetic elements in the field of the category. The chemical express the analysis of slime revealed iron availability. It should be noted that the magnetic fraction is present at slime and in case of food of a cell alternating current.

 

 

The analysis of oscillograms of tension and current in the electric chain feeding the plazmaelectrolytic cell was the following step.

 

  

 

Lower ray relates to the stress, upper to the current. It is evident in the represented oscillograms that at the moment of ceiling voltage, at the apex of sinusoid, goes the high-frequency splash of current, which exceeds its ohmic amplitude into 5-7 times. During the correct selection, with the aid of the voltage divider, the sensitivity of signal it is possible to dispose so that is begun visible the short high-voltage thrust of stress. The splashes of current and the thrusts of stress appear simultaneously. Oscillogram of a change in the line voltage of the nourishment of plazma elektrolytic reactor.

The voltmeter at that moment showed stably the current of 220 volts.  

 

Most of researchers, who study plasma electrolysis, prefer to work with the cathode plasma. From one side because to excite plasma on the cathode more easily for technical reasons, since the relatively low current density is required for this. From other side, judging by the spectrum, cathode plasma is ionized hydrogen. With the small thickness of plasma sheath and accelerating voltage into hundreds of volts, the energy of the protons, which bombard cathode, can reach the significant magnitude. This also entices the authors, who assume that are under such conditions possible the reactions of cold synthesis on the cathode (which, by the way, and is confirmed experimentally). However, separate works are dedicated to the study of anodic plasma. In particular, Bazhutov Y.N. describes his experiments on the excitation of plasma on the tungsten anode. His installation consisted of the glass cell with the electrolyte, placed into the capacity with the cooling water. In the cell they placed cathode made of the sheet stainless steel and tungsten rod, which is been the anode. The solution of alkali salts in the light water with different additions of heavy water was used as the electrolyte. With the work of cell with the electrolyte of 7M KF (50% OF D2O) was observed interesting and strange phenomenon. Approximately from the 40th minute of plasma electrolysis, in the reservoir of cooling, from the side of the anode water began to lose its transparency. Cooling cell water, which is been located from the side of cathode, remained transparent. Radiation background remained in this case constant. Impression was created, that, water was saturated by metastable microscopic gas bubbles. The transparency of water was restored only 10 hours after the end of experiment. The authors assume that they observed action on the water of a certain corpuscular (or electromagnetic) flow of unknown nature from the side of the plasma anode.

 

 We revealed the possibility of the excitation of anodic as well as cathode plasma and essential influence of inductance in the feed circuit of electrolytic cell.

 

Brief conclusions: 

 

1) Actually, with the plasma electrolysis a quantity of hydrogen being isolated exceeds current output in the alkaline electrolyte (Na2CO3) 1, 7-2, 2 times. In the acidic (H2SO4) 2, 5-3 times. As noted in the work of Kanareva F. M. and T. Mizuno exceeding along the current of the yield of hydrogen 10-20 times in our experiments was not reached. 

2) The calometric measurements of the releasing heat (without taking into account energy of the isolated gases) showed that the relationships of the inserted electrical energy and the obtained thermal (in the cathode plasma) have on the average of relationship 1/1, 4. 

3) The nature of excess thermal energy is seems to be connected with ionization and recombination of hydrogen.

 

 

2

 

Studies in period from July 2008 till May 2009 have opened practical possibilities for applying the systems of plasma electrolysis in heat engineering. Since that time basic difficulty consisted in the exception of the erosion of electrodes. This is directly connected with the operating characteristics of aggregate. After giving a certain preference to anodic plasma, we found physical conditions, with which plasma electrode did not undergo noticeable wear. The moments of the anomalous behavior of anodic plasma were also revealed. Anomaly, as we count, consists of the following. On the stated below diagram, with the connection of increment load (incandescent lamp) in parallel into the direct-current circuit, is observed decrease in the consumed current in the ammeter of a1. With the power of the combustion of plasma into 1kVt is allowed the connection of increment load to 300 of watts. The capacitors of s1 and S2 must exceed capacity above 250- TI F, with the inductance of choke 0, 1 H. With the connection of increment load it is more than 300- t of watts, becomes noticeable influence on the plasma, in the form its “attenuation”. Calometric measurements in the cell without the energy content of the isolated gases and to the increment load in the form of incandescent lamps; they showed the relationship of the inserted electrical energy and by the obtained thermal as 1/1.

 

 

 

  At the "ignition" of the cathode plasma, under this scheme, this effect was manifested in a very small degree.  Incandescent  lamps  were barely smoldering, and in the case of the anode plasma  their light was above its rated operation. Without burning plasma the  incandescent lamps were not lit, because capacitors in the circuit do not pass direct current. The presence of plasma gap in the chain contributes to the appearance of the variable component of which, apparently, is reflected in the emergence of "interesting" effects. Thermal measurements of plasma showed that the preference should be given to cathode plasma as, cathode plasma generates by 20-40% more heat, than the anode one. Besides, release of hydrogen as fuel, in cathode plasma it is more than when the cathode is simply a metal plate. Except this advantage it is necessary to consider that cathode plasma works almost silently, "softly". Anode plasma emits the sharp, sometimes rattling sound.

 

Our experiments