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12. PLASMA ELECTROLYSIS OF WATER

 

12.1. Plasma - Electrolytic Process

 

Electrolytic processes are known for a long time, and they are widely used in chemical industry. Plasma - electrolytic processes have been found quite recently, thats why there is neither physical, no chemical theory of these processes. The preliminary analysis shows that a complete description of plasma - electrolytic process can be based neither on purely physical notions, nor purely chemical ones. These are interconnected physical and chemical processes, thats why it is possible to subdivide them into physical processes and chemical ones only conditionally.

A plasma - electrolytic reactor is a device, which is made of dielectric material (Figures 85-88). The working solution is fed into the space between the electrodes. If voltage is increased it results in the change of strength of current in a chain, which characteristic appropriateness is shown in Fig. 84.

 

 

 

 

Fig. 84. Volt - ampere characteristic, which corresponds to Table 38

 

 

Table 38. Test results of reactor No. 1 when 8.74 litres per hour of 1-normal solution HCl is consumed. its temperature at the input being 23.0C

 

Rated points

Voltage, V

Current, A

Input

Energy, kJ

Temperature of the solution, C

Output Energy, kJ

Index efficiency,%

1

2

3

4

5

7

9

1

10

1.7

61.2

24

36.6

59.8

2

40

8.2

1180.8

49

952.1

80.6

3

58.5

9.15

1927.0

73

1831.0

95.0

4

80

7.85

2260.8

82

2160.6

95.6

5

100

6.65

2394.0

83.5

2215.5

93.0

6

102

3.75

1377.0

81

2121.1

154.0

7

85

4.7

1438.2

69

1684.5

117.1

8

76

4.3

1176.5

65

1538.0

130.7

9

68.5

3.75

924.7

55

1171.8

126.7

10

88

4.5

1425.6

71

1757.8

123.3

11

92

4.2

1391.0

71

1757.8

126.4

12

94

4.4

1489.0

71.5

1776.1

119.3

13

98

4.2

1481.8

71

1757.8

118.6

14

68

3.9

954.7

56

1208.5

126.6

15

64

3.3

760.3

50

988.7

130.0

16

61

3.05

669.8

46

842.3

126.0

17

57.5

9.3

1925.1

72

1794.4

93.2

 

 

Strength of current is increased when voltage is increased linearly according to Ohms law. If voltage exceeds 40 V, Ohms law is violated; if voltage is about 100 V (points 5-6), strength of current is increased spasmodically, and a bright glow (plasma) appears near the cathode. Further compulsory reduction of voltage (points 6-15) changes strength of current insignificantly. When voltage is about 60 V (points 14-15), the cathode glow disappears, strength of current is increased spasmodically almost up to the former value [71], [81], [109], [189].

Note: energies of released hydrogen and oxygen as well as emitted light have not been taken into account.

As hydrochloric acid has taken part in the process, well need binding energies of valence electron of chlorine atom during the analysis. Ionization potential of the first electron of chlorine atom is = 12.967 eV, and its binding energy with the atom corresponding to the first energy level is = 15.548 eV

 

 

Table 39. Spectrum of the 1th electron of chlorine atom and its binding energy with the nucleus

 

Quantum number

n

2

3

4

5

6

(exper.)

eV

9.08

11.25

12.02

12.34

12.53

(theor.)

eV

9.08

11.24

11.99

12.34

12.54

(theor.)

eV

3.28

1.46

0.82

0.52

0.36

 

 

 

 

12.1.1.    Physical Model of Plasma - Electrolytic Process

 

In order to find out the physical model of the process, it is desirable to observe how it takes place. For this purpose a special reactor was manufactured, which cathode chamber was made in the form of a hole in flat acrylic plastic with the thickness of 24 mm. The needle cathode made of tungsten was introduced in the hole from above, and working solution was fed from beneath and arrived from a side hole. Transparency of acrylic plastic allows to watch some details of the plasma - electrolytic process in various modes of the reactor operation. Prior to describe the observation results, let us characterize the main participants of the plasma - electrolytic process: the electrons, the protons, the atoms, the ions and water molecules.

Earlier we have shown that the electron radius is its main geometrical parameter. It is equal to Compton wave-length (172), and it is changed insignificantly during energy transitions of the electron in the atom. We have found out that the proton radius is equal to (230). It is by three orders of magnitude less that the electron radius [109].

Hydrogen atom is the next participant of the process. Its size is variable. It is increased with the temperature increase of the environment, which surrounds the atom. When the electron in the atom is on the first energy level, the distance between the proton (atomic nucleus) and the electron is equal to (240), i.e. it is equal approximately to one Angstrom. The size of hydrogen atom in non-exited state is by five orders of magnitude greater than the proton and by two orders of magnitude greater than the size of the electron. When the electron goes to the third energy level, the distance between it and the proton in hydrogen atom is increased and becomes equal to 9.5410-10 (244).

We have founds out that the sizes of all atoms in non-exited state are near to the size of hydrogen atom. Consequently, the size of oxygen is near to one Angstrom. The sizes of the ions (we do not consider the proton as the ion) and the molecules are several times greater than the sizes of the atoms and depend of the numbers of energy levels, on which valence electrons uniting the atoms into the molecules are situated.

Let us consider the structure of water molecules (Figs 72-74) and binding energies of the electrons with the nuclei of the atoms of hydrogen, oxygen and chlorine (Table 35, 36, 39). It means that a separation of the hydrogen atom and one proton from water molecule and from the molecule of hydrochloric acid (HCl) are the phenomena of equal probability, because they have similar binding energies on energy levels of the same name.

If we analyse the data of Fig. 84 and Table 38, we can form the following physical model of plasma - electrolytic process. When voltage is increased up to 60 V, a well known ion conductivity operates in the solution. At such potential water molecules contacting with the cathode by positively charged protons of hydrogen atoms dissociate into molecular hydrogen and hydroxyl ions (Fig. 75). In this case a usual process of water electrolysis takes place [109].

When voltage is increased, hydrogen atoms and their protons begin to be separated from water molecules. At first separate streamers (sparks) appear in the solution near the cathode. It points out to the fact that the protons of hydrogen atoms are separated from water molecules and during their movement to the cathode are united again with the electrons producing new atoms of hydrogen. Further increase of voltage increases quantity of the protons, which have been separated from water molecules, and plasma of hydrogen atoms is formed near the cathode (points 5, 6). The electrons of hydrogen atoms are in an exited state at this moment and move from high energy levels to low energy levels generating the light of Balmier spectral lines. One can judge by intensity of these lines, between which energy levels of hydrogen atoms the largest quantity of electron moves.

Visual analysis of the whole spectrogram (only a part in shown in Fig. 81) demonstrates that the largest quantity of electrons in hydrogen atoms moves from the third to the second energy level (the light bright band to the left of Fig. 82). The light zone near this band to the right confirms the simultaneous formation of hydrogen molecules [60], [61], [62].

As voltage is reduced (points 7-14) the volume of plasma is reduced, energy levels of the electrons of hydrogen atoms, on which they stop, move off from the protons, energy of emitted photons is reduced, wave-length is increased, and colour of plasma is charged from bright white to red. Then the moment takes place (point 15) when the potential on the electrons is not enough for the separation of the protons from water molecules, and the process goes out slowly returning the system into the initial state of ion conductivity (Fig. 84).

If we analyse Table 38 and Fig. 84, we see that the data on the mode corresponding to point 6 are of the greatest interest. This mode has been formed spontaneously. Stable plasma is absent in point 5, only glimmer can be observed near the cathode. Then in a certain period of time current is reduced spontaneously, and stable plasma appears at once.

Plasma being formed limits the contact of the solution with the surface of the cathode (it increases resistance in cathode - solution circuit). As a result, the value of current is reduced sharply and remains such till energy of plasma and applied voltage is enough for the separation of the protons from water molecules.

Hydrogen atoms unite into molecules on plasma - solution boundary. Their further fate depends on availability of oxygen atoms. If they exist, water molecules are formed with the characteristic micro - explosions, which generate noise in some modes of the reactor operation. If there are no oxygen atoms near the cathode or they have been united into oxygen molecules, hydrogen molecules are mixed with oxygen molecules and form the so-called blasting mixture, which is removed from the cathode together with water vapours.

If voltage is increased after appearance of plasma (Fig. 84, point 6), plasma temperature is increased, and the spike of tungsten cathode becomes bright white at first, then it starts burning. It is easy to observe this process through transparent acrylic plastic of the reactor. The larger voltage, the more intensive is burning (melting) of the cathode. It is known that melting point of tungsten is 3382C, and its boiling point is 6000C.

Thus, atomic hydrogen is a source of plasma in plasma - electrolytic process. Alternating electric field keeps hydrogen atom in an exited state forming its plasma with the temperature of (5000...10000)C. Intensity of this plasma will depend on applied voltage and on the consumption of the solution, which flows about the cathode. The greater applied voltage and the greater the consumption of the solution, the more intensive plasma is.

 

 

 

12.1.2.    Chemical Model of Plasma - Electrolytic Process

 

Starting to consider a chemical model of the plasma - electrolytic process we have to point out that modern chemistry does not know an abundance of energy levels of each electron and an abundance of binding energies between the atoms in the molecules. We do not know how the values of binding energies of hydrogen atoms with oxygen atoms in water molecule have been obtained before our investigations (with the help of the calculations or experiments), but we have shown that these energies do not correspond the energies of dissociation of water molecules during its low voltage electrolysis, i.e. they do not correspond to energy consumption during water decomposition into hydrogen and oxygen. We are faced with the problem: what to do next? Shall we trust these and other calculation results of modern chemistry or shall we cast doubt on them?

As atomic hydrogen exists at the temperature of (5000...10000)C [52], plasma with such temperature is formed in the cathode zone. Plasma will exist only under the condition of sufficient density of hydrogen atoms in the given volume. In order to fulfil this condition it is necessary to increase density of current on the cathode. After the formation of hydrogen atoms or their separation from water molecules they would remain in non-exited state if there were no external influence. But during the operation of the plasma - electrolytic reactor hydrogen atoms are at continuous influence of alternating electric field, which makes hydrogen atoms be in exited sate, it is proved by availability of a complete set of Balmier spectral lines on a spectrogram. Unfortunately, we have no complete spectrum of hydrogen atom and know nothing about availability of Limon spectral lines, Pashen spectral lines, etc., it makes the analysis of the phenomenon being studied difficult [109].

The following chemical reactions will take place in the plasma solution interphase boundary at the same time

 

. (292)

and

(293)

 

If a molecule of oxygen is formed near the anode, energy is released

 

(294)

 

In the model of the reactor, which trial results are given in Table 40, hydrogen and oxygen escape via the same branch pipe, thats why endotermic reactions are possible in it [2]

 

1- formation of hydrogen peroxide

 

(295)

 

2 - formation of ozone

(296)

 

3- formation of the ion of hydroxonium

 

(297)

 

Unfortunately, we do not know intensity of both exothermic (292, 293, 294) and endothermic (295, 296, 297) reactions. Solution temperature change regularity (Table 38) points out to the fact that intensity of endothermic reactions in the zone of existence of molecular hydrogen (points 3, 4, 5) is lower than in points 7-15 where plasma of atomic hydrogen is preserved, and solution temperature is reduced. The reduction of water temperature during voltage decrease in the experiment (Table 38, points 6-15) is explained by intensive absorption of heat during the formation of hydrogen peroxide , ozone and ion .

The Japanese investigators Ohmori and Mizuno found dissemination of nickel, chromium and carbon on the cathode of the plasma - electrolytic reactor [51]. To their mind, cold nuclear fusion is a source of these chemical elements. Later on well analyze this phenomenon in detail.

 

 




       
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The Foundations of Physchemistry of Microworld

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