<<
Back to Kanarev's Physchemistry Book Index
11. NEW THEORY OF LOW VOLTAGE ELECROLYSIS OF
WATER
11.1.
Contradictions of the existing
theory of water electrolysis
American scientists Fleishmann and Pons have reported about obtaining of
additional energy during water electrolysis in 1989 year and about the fact
that cold nuclear fusion is the source of this energy [67]. Hundreds of
experiments were made in various countries in order to check this fact [23],
[28], [50], [51], [65], [67], [73], [79], [83], [103]. A part of the scientists
confirmed it, and another part received a negative result [67], [74]. The cause of such state remains unclear. That’s why let us analyse the
water electrolysis process once again and try to make out with the essence of
the processes, which take place [109].
The results of the
given experiment put the main question: by which physical and chemical
phenomenon is additional energy generated during usual water electrolysis? The
first hypothesis: nuclear fusion at low temperature (cold nuclear fusion) is
being checked from 1989 year, but still it has no definite confirmation [67],
[76]. The second hypothesis assumes that there is a certain particle
called “ersion”, which is responsible
for the emergence of additional energy [77]. But the main characteristics of
this particles remain unknown, that’s why it is necessary to check one more
hypothesis: additional energy is extracted from energies of chemical bonds of
water molecules.
The main purpose of
electrolysis of water is obtaining of
hydrogen, which is considered to be the most prospective energy carrier
in the future [39], [41], [49], [56], [57]. It has been discovered quite
recently that in some cases access energy is released when this process takes
place [67]. If we want to find out its reason, we should analyses a classical
method of hydrogen production by means of water electrolysis. It is described
in reference books. Chemical reactions, which take place during this process,
are used for the calculations of its parameters. They are considered to be
clear and do not give rise to objections of both chemists and physicists. Let us consider if it is
actually clear.
Cathode and anode
reactions are described in the manual in such a way [2]. “The following
reaction takes place at the cathode
(257)
Two electrons,
which have arrived from the cathode, react with two molecules of water forming
hydrogen molecule 
and two ions of
hydroxyl 
. Molecular hydrogen forms the bubbles of gaseous hydrogen
(when the solution near the cathode has been saturated with hydrogen), and the
ions of hydroxyl remain in the solution.
The following
reaction takes place at the anode
(258)
Four electrons come
to the anode from two molecules of water which is decomposed with the formation
of an oxygen molecule and four ions of hydrogen.
Total reaction can
be obtained if the equation (257) is multiplied by 2 and added together with
the equation (258). It is put down in the following way
(259)
… in acid solutions
with a high concentration of hydrogen ions, the following reaction cam take
place at the cathode
(260)
Let us close
quotation marks and put the following question: how should be the symbol 
interpreted in this
description of the essence of electrolysis process? Naturally, 
means positive ion of
hydrogen atom, i.e. proton. But the chemists have managed to designate a
positively charged ion of hydroxonium 
with the same symbol.
They have come to an agreement: to write 
instead of 
for the purpose of
simplification. We have nothing but guess: should we always understand a
chemical symbol 
as a set
of symbols 
or no? If
so, how should we distinguish the cases “yes” and “no”? Symbol 
is used in
many other chemical reactions. We should note that it is not the author of the
above-mentioned manual who should be blamed, he has acted in the way as others
act.
If we agree with
the process of electrolysis described in the given manual, it means that water
solution has protons, which are designated with the help of the symbol 
by the author. As
they have a positive charge, they move to the cathode; having obtained electron
from it, they form
hydrogen atoms 
, which, being connected, form the molecules 
. It is impossible to interpret the formula in another way
(258) and (260).
Besides, it appears
from the formula (258) that at the anode the fusion process of the oxygen
molecules from its atoms takes place, which should be accompanied by release of
energy of 495 kJ/mole [2]. It should be
taken into account during the analysis of energy balance of water electrolysis
process, but in modern chemistry they are not accustomed to carry out such
analysis, because it gives lots of contradictions with the experiment.
The first
contradiction. Let us introduce symbol 
for the designation
of the proton only, as it should be. The hydrogen atom formation reaction is
written in the following way
(261)
The hydrogen
molecule formation reaction is presented in the following way
.
(262)
The hypothesis
concerning the presence of free protons in various chemical solutions is
frequently used in chemistry. By the appearance of plasma electrolysis of water
casts doubt on this hypothesis. The matter is that the proton is an active
formation, which can exist only in the composition of various chemical compounds.
If the conditions are created under which the proton is separated from the
chemical compound, it lacks the existence phase in the free state almost
completely. Having separated from one chemical element, it unites with other
one at once.
Evidently there are such
conditions when the proton of hydrogen atom having separated from water molecule
is connected with the electron emitted by the cathode and forms hydrogen atom.
It is known that hydrogen atoms exist at the temperature of 5000…10000°C [52]. It means
that plasma with such temperature should be formed at a certain density of
hydrogen atoms in the unit of volume. As it
is known, no atomic hydrogen plasma is formed during low-voltage electrolysis
of water. It means that there is no atomic hydrogen fusion process in this
case.
Hydrogen molecule
fusion energy (436 kJ/mole) is known in modern chemistry, that’s why we can
calculate approximate quantity of
energy, which should be released in electrolytic solution during
production of one cubic meter of hydrogen [2], [32], [52].
One cubic meter of
hydrogen contains 1000/22.4=44.64 mole of molecular hydrogen. Energy is released
at its fusion
. (263)
Modern
electrolyzers consume nearly 4 kWh of electric power or (3600 x 4)=14400 kJ for
obtaining one cubic meter of hydrogen. Taking into consideration energy
(19463.0) of fusion of one cubic meter of hydrogen and energy (14400) consumed
by its production, we shall find water electrolysis process efficiency index
(264)
Thus, a simple and
rigorous calculation shows that the process of low voltage water electrolysis
should be accompanied by a release of 35% of additional heat energy in the
cathode area only.
Let us pay
attention to the fact that this index takes into consideration only energy of
the fusion of hydrogen molecules and does not take into account energy of the
fusion of hydrogen atoms as well as energy content of produced hydrogen.
Efficiency index
(264) confirms the possibility of obtaining of additional energy, but only
under the condition that electrolysis of water is accompanied with fusion
process of hydrogen molecules. Lack of additional energy in the operation of
modern industrial electrolyzers makes us draw an absurd conclusion (on the face
of it) concerning the lack of fusion process of hydrogen molecules from its
atoms. Later on we’ll show
that it is so indeed.
If we agree that
there is a fusion process of the oxygen molecules, the following reaction
should take place in the anode area:
, (265)
It means that the
oxygen molecules and the hydrogen atoms 
should be formed. But, as it is known, only oxygen can be
released in the anode area during low-voltage water electrolysis.
It is known that
during low-voltage water electrolysis the process of formation of 1 
(44.64 moles) of
hydrogen is accompanied by a release of 22.32 moles of molecular oxygen. As a
result, 495x22.32=11048.80 kJ of energy should be released. If we add this energy
to hydrogen molecule fusion energy, we’ll get
(266)
Total
index of energy efficacy of low-voltage process of water electrolysis should be
as follows:
(267)
It is known that
heat energy index of modern low-voltage process of water electrolysis is less
than unit. It means that there is no fusion of the molecules of hydrogen and
oxygen in this process.
A question arises:
how are the molecules of hydrogen and oxygen formed during low-voltage process
of water electrolysis? Later on, we’ll show that the molecules of hydrogen and
oxygen are released from the cluster chains in the formed conditions, i.e.
without the bond process of separate atoms and molecules.
Thus, if chemical reactions (257) and (258) took place in
modern electrolyser, they would have efficiency index more than one, ... as it follows
from the ratio (264). The lack of additional energy during the low voltage process
of water electrolysis is the result of formation of hydrogen molecules
according to the diagram shown in Fig. 78.
The second
contradiction. Now let us check the correspondence of the reality of binding energy
of hydrogen atoms in water molecules accepted in modern chemistry. Modern chemistry
theory gives values of binding energies of hydrogen atoms with oxygen atom in
water molecule, but they differ from experimental values of these energies.
For example, in the
book in chemistry [2] the following
value of binding energy 
of one hydrogen atom
(let us call it the first one - 
) with oxygen atom (
) in water molecules 
=424 kJ per mole is given [2]. Let us transform it into
electron-volts calculating on one water molecule[1]
(268)
Binding energy of
the second 
hydrogen atom with
oxygen atom (
) in water molecule 
is equal to 
=502 kJ per mole [2]. In terms of electron-volts calculating
on one bond we’ll have
(269)
If the hydrogen
atoms in water molecule have binding energies corresponding to energies given
in the formulas (268) and (269), cleavage of two bonds with energies of 4.40 eV
should result in the formation of the hydrogen molecule; an oxygen molecule
should be formed when two bonds with energies of 5.21 eV are broken. The energy
expenses for the formation of one cubic meter of hydrogen and oxygen being
obtained will be 424.00х44.64=18927.36 kJ and 502.00х 22.32= 11204.64
kJ, respectively. Total energy expenses for production of one cubic
metre of hydrogen will be 18927.36+11204.64=30132.00 kJ or 30132.00/3600=8.37
kWh.
It is twice as much of the experimental value. Consequently, the
above-mentioned (268)
and (269) binding energies
of the hydrogen atoms with the oxygen atom in water molecule do not correspond
to reality.
In which
experiments are the above-mentioned binding energies registered? The
experiments connected with water electrolysis and spectroscopy are the most
congenial. Let us take minimal expenses of energy for hydrogen production
established experimentally 3.8 kW×h per 
. Let us represent this energy in terms of kJ. 3.8x3600=13680
kJ. Taking into account the fact that molar volume of all gases is similar and
is equal to 22.4 L, we’ll find quantity of moles of molecular hydrogen in one cubic
meter of hydrogen 1000/22.4=44.64 moles. Energy consumption per mole of
hydrogen is 13680/44.64=306.45 kJ and per molecule
. (270)
In order to form
the hydrogen molecule during water molecule destruction, at least two bonds of
water molecules should be destroyed; it means that mean energy per bond is
3.18/2=1.59 eV. The value does not match the result given the formulas (266)
and (267). If we take into account inevitable energy losses during
electrolysis, we have every reason to believe that energy 1.59 eV is congenial
to binding energies of the electron in hydrogen atom (Table 5) when it is on
the third energy level (1.51 eV). It is congenital to binding energy of the
eight electron in oxygen atom (1.53 eV) when it is on the similar energy level
(Table 21). It results in almost equal probability of separation of both
protons and hydrogen atoms from water molecules. The detailed analysis of this
process will be given below.
Thus, the
above-mentioned tables have no binding energies, which correspond to the existing
calculations of chemists (266), (267); vice verse, these tables contain binding
energies resulting from out calculation of the existing process of water
electrolysis.
So, we have every
reason to believe that the electron in
the first atom of hydrogen 
in water molecule and
the 1th electron in oxygen atom are on the third energy levels.
As it is clear,
existing theoretical chemistry has serious contradictions with an experiment,
but chemists avoid the search of the reason of these contradictions, they do
not take into consideration the arising questions. The answers to them can be obtained
from the analysis results of water molecule structure [46].
We’ll not find the
answers to these questions within the framework of existing physical and
chemical notions concerning the structure of water molecule and the process of
its electrolysis, that’s why we have only one possibility: to pay attention to
the own results of the investigations in this field [8], [12], [13], [17],
[18], [26], [33], [53], [70], [75], [109] and to take the water molecule
structure, which originates from the
atomic nucleus structures, of hydrogen (Fig. 50, a) and oxygen (Fig. 61), as
the basis.
The
Foundations of Physchemistry of Microworld
Copyright Ó2003 Kanarev Ph.
M.
Internet Version - http://book.physchemistry.innoplaza.net
<< Back to Physchemistry Book Index
