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Water dissociation in a radio-frequency electromagnetic field with ex situ

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DOI: 10.1088/0963-0252/22/1/015010

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Plasma Sources Sci. Technol. 22 (2013) 015010 (8pp) doi:10.1088/0963-0252/22/1/015010

Water dissociation in a radio-frequency

electromagnetic field with ex situ
electrodes—process characterization
Jens Schneider, Frank Holzer, Markus Kraus, Frank-Dieter Kopinke and
Ulf Roland
Helmholtz Centre for Environmental Research–UFZ, Department of Environmental Engineering,
Permoserstr. 15, 04318 Leipzig, Germany
E-mail: frank.holzer@ufz.de and ulf.roland@ufz.de

Received 9 August 2012, in final form 22 October 2012

Published 13 December 2012
Online at stacks.iop.org/PSST/22/015010

Abstract
A new type of water dissociation at ambient pressure initiated by the irradiation of aqueous
electrolytes using an electromagnetic field with a frequency of 13.56 MHz is described in this
study. A special reactor design allows the use of ex situ electrodes to form in situ electrical
discharges in water vapour bubbles. The observed formation of molecular hydrogen (H2 ) and
oxygen (O2 ) combined with the emission of light (‘burning water’ phenomenon) originates
from a non-thermal plasma in water vapour bubbles. The influences of type of electrolyte, its
concentration, pH value and external RF voltage on the gas formation rate as well as on the gas
composition are presented.
(Some figures may appear in colour only in the online journal)

1. Introduction The idea of using external electrodes for water dissociation

The use of radio-frequency (RF) electromagnetic fields in order
to dissociate water has been recently described by several
research groups [1–5]. It was shown that exposing distilled
water or solutions containing an electrolyte such as dissolved
NaCl to an RF field can lead to the generation of H2 , O2 and
H2 O2 . Thereby, the use of rods with internal gas flow [1, 2],
rod and spherical plate electrodes with dielectric barrier [3] as
well as mesh and plate electrodes within or in direct contact
with the solution [4] are described as employed experimental
setups. However, even more widely used for the initiation
of discharges in water are pulsed direct- (dc) and alternating-
current (ac) voltages mostly in combination with needle or
rod electrodes. The review papers [6, 7] give a wide overview
of experimental setups for electrical discharges in water and
above the water surface.
A new concept is the application of specifically designed
antennas placed outside of the solution which produce a
focused RF field with a frequency of 13.56 MHz [8]. In this
case, H2 and O2 are produced on the surface of the solution.
The basic mechanism of this new phenomenon (‘burning
water’) cannot yet be clarified.
is rather interesting since the known problems of electrode
corrosion could be overcome with such an approach.
Furthermore, discharges in pure water vapour avoid energy
losses known from discharges in non-inert gases (e.g. air) and
the formation of undesirable products (e.g. NOx in the case of
air discharges).
This study in some respects represents a combination of
external electrodes with the capillary reactor design [9, 10] to
realize a new kind of water scission. This concept allows
us to create a gas phase consisting of pure water vapour
in situ representing an alternative to discharge formation in
water-saturated (inert) gases or bubbles formed by external gas
dosage [3, 11]. The solution surrounding the bubbles formed
in situ practically acts as electrode assembly. The current
densities in the film between bubble and glass tube are strongly
increased in accordance to the capillary reactor design [9, 10]
which is a prerequisite for the formation of discharges.
This paper presents a novel glass reactor design allowing
us to focus RF energy to a restricted volume of an aqueous
electrolyte, enabling selective heating, in situ formation of
water vapour bubbles and initiation of electrical discharges in
these bubbles leading to H2 and O2 generation. A water column

0963-0252/13/015010+08$33.00 1 © 2013 IOP Publishing Ltd Printed in the UK & the USA
Plasma Sources Sci. Technol. 22 (2013) 015010
Figure 1. Reactor type I (left) and reactor type II (right) made of
duran and quartz, respectively, with emphasis on the restriction.
remaining above the discharge zone acts as transfer medium
for the unconsumed oxyhydrogen gas. This concept uses a
plate electrode system outside of a glass reactor. Thus, the
electrodes are not in direct contact with the aqueous solution.
2. Methods
2.1. Basic setup
A water-cooled RF generator (PFG 1000 RF, Hüttinger
Elektronik, Freiburg/Brsg.) working at a fixed frequency of
13.56 MHz and having a maximum power of 1 kW was used
in combination with an impedance adjustment network (PFM
3000A, also from Hüttinger). This so-called matchbox con-
tains adjustable vacuum capacitors and coils to reduce energy
reflection from the load to the generator. The electrode sys-
tem consisted of two parallel copper plates. One electrode was
connected to the RF matchbox output supplying a maximum
voltage of 2 kV while the other was connected to the ground
and the Faraday cage utilized for electromagnetic shielding.
Two glass reactors, both with an inner diameter of 12 mm
(outside of the restriction) and a wall thickness of 1.5 mm,
one consisting of duran (type I, figure 1, left) and the other
consisting of quartz (type II, figure 1, right), were employed.
The lower cylindrical and U-shaped parts of the two reactors
shown in figure 1 were placed between the parallel plate
electrodes while at least one tube end left the shielding cage.
The reduced inner diameter in the restriction of the glass tubes
was about 3 mm (magnification, figure 2).
On top of the reactor tube leaving the Faraday cage a water
cooler was installed followed by a glass vial for gas sampling.
Figure 2 shows a scheme of the whole experimental setup.
2.2. Analytical methods
A gas chromatograph (GC) coupled with a thermal-
conductivity detector (Agilent GC System 6850A; column
HP-PLOT, 30 m × 0.32 mm × 12 µm) was used to identify
and quantify H2 , O2 , N2 , CO and CH4 concentrations in the
product gas. Another GC coupled with a mass spectrometer
2
J Schneider et al
Figure 2. Scheme of the experimental setup emphasizing the
geometry of the restriction.
(MS) (Shimadzu GC-17A/MS-QP5000; column Agilent DB-
1, 60 m × 0.32 mm × 5 µm) was used to identify additional
products in the gas and liquid phases.
For temperature measurements in the RF field, two
different methods were used. Firstly, fibre optical temperature
probes (Nortech or Neoptix, Quebec) directly quantified
the temperature at different positions within the electrolyte
solution. Secondly, an infrared (IR) thermo-camera
(VarioTHERM, Infratech, Dresden) allowed measuring either
the outside surface temperature of the reactor wall or, using a
special ‘through-glass filter’, the temperature of the electrolyte
solution in a defined region.
2.3. Chemicals
Electrolyte solutions were prepared by adding the respective
chemicals with purities of more than 99% provided by Merck
to deionized water with a residual specific conductivity of
<3×10−4 S m−1 . All conductivities were measured at 22.5 ◦ C.
3. Results and discussion
3.1. Phenomenological description
When an electrolyte solution in the glass reactor was exposed
to a sufficiently strong RF electromagnetic field, generally the
following three phases could be observed. First, selective
heating of the solution within the restriction, caused by the
occurring high current densities, was observed. Subsequently,
when local temperatures within the heated volume of the
restriction reached the boiling point of the solution, water
vapour bubbles were formed periodically with increasing
frequency. Finally, after establishing a quasi-stationary
vapour bubble positioned in the tube restriction, a continuous
discharge accompanied by gas formation of molecular
hydrogen and oxygen and emission of light occurred. A
photograph of such a discharge obtained when using a NaCl
solution with a concentration of 5 weight per cent (wt%) is
presented in figure 3.
Plasma Sources Sci. Technol. 22 (2013) 015010
Figure 3. Discharge in the restriction of the reactor using a 5 wt%
NaCl solution as electrolyte.
Figure 4. IR image of the glass reactor (restriction region) during a
steady-state plasma discharge (1.9 kV, 600 W RF power, 5 wt%
NaCl electrolyte). Positions of the fibre optical probes are marked
as white dots: 1—above restriction, 2—upper part of restriction,
3—lower part of restriction and 4—below restriction.
3.2. Selective heating
The IR camera was used to demonstrate the selective heating
of the electrolyte solution in the restriction of the reactor tube.
Figure 4 shows an example for such an IR image. These
measurements confirmed the occurrence of bulk temperatures
of more than 240 ◦ C when discharges were running. The IR
camera produced five pictures per second showing that this
high-temperature region occurred at different positions within
the restriction indicating local fluctuation of the plasma. In
addition to IR observations, four fibre optical probes were
placed in the glass reactor as indicated by white dots in figure 4.
Figure 5 gives an example of typical temperature evolution
within the solution at these four measuring positions in
the restriction range of the reactor. Three of the four
probes detected temperatures approaching 100 ◦ C. One sensor
(lower part of the restriction) detected temperatures >250 ◦ C.
Unfortunately, the measuring range of the applied fibre optical
3
J Schneider et al
Figure 5. Temperatures at different positions in and close to the
plasma zone (conditions as specified in figure 4).
probes was limited to temperatures lower than 270 ◦ C such
that the true temperature could not be directly measured. The
distinct local temperature differences indicate the presence of
hot spots in the plasma zone.
After establishing a quasi-stationary water vapour bubble,
the two temperature sensors in the restriction were permanently
situated in the gas phase. The sensor in the lower part of the
restriction seemed to be in contact with discharges at the gas–
liquid interface explaining the high temperatures >250 ◦ C.
At the same time, the second sensor in the upper part of
the restriction did not show temperatures >100 ◦ C though it
shared the same gas phase as the probe no 3. Due to the
limited temporal and spatial resolution of the IR camera and
the fibre optical sensors, the measured temperatures have to
be considered as mean or effective values. Actual values can
even be higher. In spite of these locally high temperatures it is
postulated that the formation of hydrogen and oxygen as well
as the emission of light originates from plasma which is in its
nature non-thermal but not necessarily ‘cold’ plasma. Electron
impact processes governing this plasma were at the centre of
a study that will be published in a forthcoming paper [12].
Although relaxation processes connected with ‘thermalization’
lead to measured temperatures of at least about 300 ◦ C in the
discharge, the identified large electron energies above 10 eV
are a clear indication for the non-thermal nature of the plasma.
3.3. Vaporization of water
Two experiments applying the reactor type II were used to
study the frequency of bubble formation with 5 wt% NaCl
solutions that contained no surfactant or 1.8 g l−1 of sodium
dodecyl sulfate (SDS) at RF voltages of 1.3 and 1.9 kV (300
and 600 W RF power, respectively). The surfactant SDS was
used to analyse if the surface tension of the solution has an
influence on bubble formation and gas formation rates. An
optical camera recording 30 pictures a second was applied to
observe bubble formation in the restriction of the reactor and
to calculate its frequency. RF power was applied to solutions
at a temperature of 25 ◦ C before each measurement. Time
Plasma Sources Sci. Technol. 22 (2013) 015010
Figure 6. Frequency of bubble formation at RF voltages of 1.3 and
1.9 kV for 5 wt% NaCl solutions with (open symbols  , ◦) and
without (filled symbols , •) 1.8 g l−1 SDS. Straight lines represent
linear fits.
recording started after the first bubble was observed. The
frequencies of bubble formation are shown in figure 6.
As expected, at 1.9 kV, bubbles in the restriction appeared
faster after RF power activation and with a higher frequency
than at 1.3 kV. The frequency increased with progressing time
after switching on RF power as the mean temperature of the
solution in the vicinity of the restriction increased.
The addition of the surfactant SDS to the solution led to
a higher starting frequency of bubble formation, as shown
in figure 6. Due to reduction in the surface tension of the
electrolyte solution, formation of phase interfaces is facilitated.
The increase in frequency with time was also enhanced by
addition of SDS.
Electrons of energies lower than 100 eV which are likely
present in the gas phase when discharges are initiated do not
penetrate the liquid phase deeper than a few nanometres [13].
As surfactants are enriched in the gas–liquid interface one
would expect a decomposition of SDS by electron impact or
thermal processes. And indeed, CO, CO2 and CH4 as products
of decomposition of SDS were detected in the product gas in
the range of 1 vol% and 0.1 vol% for carbon oxides and CH4 ,
respectively. But due to the fact that in comparison with NaCl
solutions without SDS overall gas composition and formation
rate (figure 7) did not change significantly, one can assume
that the gas–liquid interface does not play a significant role for
the hydrogen and oxygen formation process. In other words,
electron impact processes finally leading to the formation of
hydrogen and oxygen most likely take place in the bulk phase
of the water vapour bubble. There, the water partial pressure,
i.e. the concentration of water molecules, is not likely to be
influenced by the presence of the surfactant.
3.4. Influences on gas formation and gas composition
One of the key features of the described plasma phenomenon
is the formation of a hydrogen–oxygen gas leaving the
glass tube. Discharges were always accompanied by gas
formation in the restriction region of the glass reactor. The
4
J Schneider et al
Figure 7. Gas formation rates and H2 /O2 ratios for several
electrolytes used under similar experimental conditions
(conductivity of the solution: 5.8 S m−1 , RF voltage: 1.3 kV, reactor
type I).
observable gas formation rate was chosen as characteristic
criterion representing the intensity of the discharge. The
influence of parameters such as electrolyte type, concentration
and pH value on gas formation rates and composition are
presented below. In this study where ex situ electrodes are
applied, high electrolyte concentrations are essential to create
discharges within the voltage range of the matchbox (<2 kV).
A sufficiently high voltage drop over the water vapour bubble
necessary for discharge initiation could only be realized if the
overall resistivity of the electrolyte solution was low. This
condition seems to be valid for discharges in capillaries where
the solution itself acts as electrodes [9, 10]. In contrast, rather
low conductivities are sufficient for discharge initiation over a
water surface or with gas dosing [6, 7, 11].
3.4.1. Type of electrolyte. Electrolyte solutions with a
(low-frequency) specific conductivity of 5.8 S m−1 each were
prepared using one of the following chemicals: Na2 SO4 ,
K2 SO4 , KCl, NaCl, Na2 CO3 , Mg(ClO4 )2 , KNO3 , NaNO3 ,
HCl, HNO3 , NaOH and KOH. To ensure comparability
between the results, the electrical conductivity instead of
molar or mass concentrations was chosen as the parameter
that did not vary between the solutions. This is justified since
firstly, ohmic losses are the dominant heating mechanism in
concentrated electrolyte solutions at 13.56 MHz and secondly,
the conductivity determines the maximal field strength in the
restriction that is responsible for discharge initiation. Each
solution was filled in the reactor type I that was placed between
the electrodes and exposed to the RF field using an RF voltage
of 1.3 kV. The gas formation rates as well as the H2 /O2 ratios
of the product gas are displayed in figure 7.
Note that electrolytes such as NaNO3 and KNO3 showed
neither discharges nor gas formation. Electrolytes such as
NaOH, KOH produced different kinds of discharges with
negligible gas formation. Due to very high pH values (>13)
the quartz glass reactors were rapidly damaged in the plasma
Plasma Sources Sci. Technol. 22 (2013) 015010
zone. Other than for strong bases, nitrates seem to inhibit
plasma chemistry probably due to the formation of NOx gases.
Surprisingly, nitric acid, though also containing nitrate anions,
did not quench the plasma discharges completely.
The product gas was typically composed of molecular H2
and O2 in a molar ratio of 2 : 1. This ratio reflects exactly the
stoichiometry of water and, therefore, excludes the formation
of significant amounts of other long-living products containing
hydrogen or oxygen. As can be seen in figure 7, discharges in
electrolyte solutions exhibiting an H2 /O2 ratio of 2.0 showed
comparable gas formation rates between 6 and 8 ml min−1 .
For these electrolytes, given the term ‘stable’ electrolytes,
there seems to be no significant influence of the electrolyte
composition on the gas formation.
Discharges in electrolytes with a different H2 /O2 ratio,
namely Mg(ClO4 )2 , HCl and HNO3 , exposed lower gas
formation rates between 3 and 5 ml min−1 . An H2 /O2 ratio
deviating from 2.0 indicates the participation of the electrolyte
or its reaction products in the plasma chemical reactions taking
place in the gas phase and the gas–liquid interface. These
electrolytes are termed as ‘reactive’ in the progress of this
paper in contrast to stable electrolytes producing an H2 /O2
ratio of 2.0.
The electrolytes HCl and HNO3 produced H2 /O2 ratios
only slightly deviating from 2.0. HCl has a significant partial
pressure in the vapour phase equivalent to a concentration
of a few 100 ppm at 100 ◦ C dependent on its concentration
[14]. Moreover, HNO3 exhibits partial pressures like HCl
[15] and is subject to thermal or light-induced decomposition
leading primarily to the formation of NO2 , H2 O and O2 [16].
Interactions, such as scavenging of electrons and/or scavenging
of oxygen and hydrogen species in the discharge zone by
electrolyte molecules and their conversion products, seem to be
responsible for lower gas formation rates and different H2 /O2
ratios.
The change in the H2 /O2 ratio was even more pronounced
for the electrolyte Mg(ClO4 )2 as a much higher O2
concentration was observed in its product gas. Although it
is known that Mg(ClO4 )2 starts to decompose between 150
and 200 ◦ C yielding additional O2 [17], this is a property of
the dry salt rather than of dissolved perchlorate. Taking into
account the decreased gas formation rate from perchlorate
solutions, it is more likely that additional oxygen species from
its decomposition scavenge molecular hydrogen or hydrogen
atoms finally yielding H2 O as product.
In addition to the substances summarized in figure 7, a
series of experiments was conducted with the two ammonium
salts NH4 Cl and N(CH3 )4 Cl and compared with the stable
electrolyte NaCl at the same concentration of 5 wt%. Note
that the gas formation rate of the stable electrolyte NaCl does
not depend on the concentration for high values >4 wt%. Both
ammonium salts exhibited markedly larger gas formation rates
and a much higher H2 /O2 ratio as compared with NaCl at the
same concentration (figure 8). This was due to an increased
formation of H2 . At the same time, the O2 formation was
strongly reduced and additional products such as N2 for both
ammonium salts and CO, CH4 and CO2 for N(CH3 )4 Cl were
observed. Traces of N2 O could be also detected for NH4 Cl.
5
J Schneider et al
Figure 8. Gas formation rates for three electrolytes in the reactor
type II (1.7 kV, 500 W RF power).
These observations prove the decomposition of the reactive
ammonium salts.
Increasing the concentration of NH4 Cl to 10.5 wt%
(conductivity >20 S m−1 ) enhanced further the rates of
formation of both H2 and N2 (figure 8). This behaviour is
different from that of stable electrolytes whose gas formation
rates remained constant above a certain conductivity level.
One can conclude that reactive electrolytes act as an educt
for plasma-chemical reactions whereas from stable electrolytes
only water is decomposed.
3.4.2. Electrolyte concentration and RF voltage. Gas
formation could be observed for a wide range of salt
concentrations but did not occur when deionized water was
used. Figure 9 presents gas formation rates in dependence on
NaCl concentration and RF voltage as measured with reactor
type II. In this study, a minimum NaCl concentration of about
0.5 wt% was found to be necessary to initiate discharges. The
gas formation rate increased almost linearly with increasing
NaCl concentration between 0.5 and 4 wt% while it was
constant within the limits of reproducibility above 5 wt%
marking a ‘saturation point’. By increasing the RF voltage,
the electric potential in the solution is enhanced. This leads to
higher voltage drops in the restriction zone resulting in higher
plasma intensities and gas formation rates.
The specific conductivity of the electrolyte solution
seems to be the appropriate parameter being relevant for
discharge initiation and intensity rather than the electrolyte
mass concentration. This could be demonstrated with solutions
of Na2 SO4 exhibiting a lower specific conductivity than NaCl
solutions at the same mass-based electrolyte concentration. As
shown in figure 9 for Na2 SO4 , the gas formation rate increased
between 2 and 10 wt% and was constant at about 13 ml min−1
at an RF voltage of 1.7 kV for Na2 SO4 concentrations above
10 wt% (saturation point).
Comparing the measurements with NaCl and Na2 SO4 ,
it can therefore be concluded that minimum solution
conductivities between 1 and 2 S m−1 are necessary for
Plasma Sources Sci. Technol. 22 (2013) 015010
Figure 9. Dependence of the gas formation rate on the electrolyte
concentration at three RF voltages in reactor type II.
Figure 10. Dependence of the gas composition (H2 , O2 and N2
concentrations) and the total gas formation rates on the
concentration of NH4 Cl (1.7 kV, reactor type II).
discharge initiation in the experimental setup and that a
constant gas formation rate is found for solutions of stable
electrolytes with conductivities >6–7 S m−1 .
Figure 10 shows the gas formation rates and composition
from NH4 Cl solutions in more detail. The concentration
of H2 in the product gas increased and the concentration of
O2 decreased with increasing NH4 Cl concentration forming a
plateau at high electrolyte concentrations. At the same time,
the concentration of N2 in the product gas was nearly constant.
Obviously, the decomposition of NH4 Cl takes place in parallel
to the water dissociation.
It can be supposed that thermal and electron stimulated
processes are responsible for the primary step of decomposi-
tion of NH+4 ions at the gas–liquid interface resulting in the
formation of ammonia gas.
NH3 can undergo various reactions with radicals and
electrons in the gas phase. Its decomposition into the
elements (equation (1)) describes adequately the measured gas
6
J Schneider et al
Figure 11. Dependence of the gas formation rate on the pH value of
a 5 wt% NaCl solution at three RF voltages.
composition (H2 : N2 = 75 : 22):
2NH3 → N2 + 3H2 . (1)
The small excess of H2 can be attributed to the water
decomposition.
3.4.3. pH value of the solution The influence of the pH value
was investigated using a 5 wt% NaCl solution in the reactor
type II and varying the pH value by adding small amounts of
HCl or NaOH. As displayed in figure 11, no significant effect of
the pH on the gas formation rates was observed. The measured
rates just scatter around an average value which depended on
the applied RF power. The molar H2 /O2 ratio was constant at
2.0 for all measurements.
This holds for an extremely broad pH range covering
about 26 orders of magnitude (!) in the H+ to OH− activity
ratio. Therefore, it can be concluded that the concentrations
(activities) of H+ and OH− ions in the solution of a stable
electrolyte do not significantly affect the plasma chemistry.
It has already been mentioned that pure hydroxide
solutions (pH > 13) yielded very low gas formation rates,
possibly caused by modifying the surface of the reactor walls
in the hot plasma zone. This may interrupt the electrolyte film
between vapour phase and glass wall so that no current can
flow through the solution. After short plasma operation times
the reactor walls were damaged.
4. Summary and conclusions
A combination of a new reactor type characterized by a
restriction in cross section and plate electrodes situated outside
of the reactor was presented. It can be demonstrated that this
setup is suitable to focus RF energy to a restricted volume of
the reactor leading to the initiation of discharges in aqueous
electrolyte solutions. Three subsequent phases—selective
heating, in situ formation of water vapour bubbles and initiation
of discharges—were observed. As a consequence of the
Plasma Sources Sci. Technol. 22 (2013) 015010
discharge processes, water molecules dissociate and H2 plus
O2 are formed as products.
Generally, electrolytes can be divided into stable and
reactive electrolytes. The first group (e.g. NaCl, K2 SO4 ) is
characterized by a molar H2 /O2 ratio of 2.0 in the product gas
and similar gas formation rates at the same conductivity. This
group comprises electrolytes that are thermally stable below
temperatures of 500 ◦ C in their pure form. Stable electrolytes
were not converted by plasma chemical processes so that
mixtures of H2 and O2 were formed.
Using reactive electrolytes (e.g. HCl, NH4 Cl,
Mg(ClO4 )2 ), molar H2 /O2 ratios deviated from a value of 2.0
and typically higher or lower gas formation rates than in the
case of stable electrolytes at the same electrolyte conductivity
were measured. Reactive electrolytes are either thermally
sensitive compounds in their pure form (decomposition
temperatures below 500 ◦ C) or exhibit a significant vapour
pressure at 100 ◦ C. Additional products such as N2 in the case
of NH4 Cl and CO, CO2 and CH4 in the case of N(CH3 )4 Cl
were formed.
The fact that thermally labile electrolytes have an impact
on plasma-chemical interactions in the discharge zone can be
seen as a hint but not as proof for the hypothesis of thermally
initiated reactions. Nevertheless, it is not yet clear where
electrolyte-converting processes occur. Decomposition might
occur thermally but also by electron impact on the gas–liquid
interface followed by subsequent transport of decomposition
products into the discharge zone. Alternatively, the formation
of electrolyte aerosols that circulate through the discharge
zone could contribute to the plasma chemistry. Since electron
impact on a surface can produce locally high temperatures
anyway, it is hard to discriminate between thermally stimulated
and electron-collision-stimulated processes. Nevertheless,
experiments with the surfactant SDS that is enriched in the
gas–liquid interface showed no significant influence on gas
(H2 and O2 ) formation. Therefore, it can be concluded that
the liquid phase which might be penetrated by electrons has no
significant influence on the oxyhydrogen formation processes.
The results presented in this work lead to the conclusion
that the electrical conductivity of the solution is the crucial
parameter that determines discharge initiation. A minimum
conductivity between 1 and 2 S m−1 (equivalent to 0.5 wt%
NaCl and 2 wt% Na2 SO4 , respectively) was required to initiate
discharges and gas formation with any electrolyte in the
experimental setup. The gas formation rate enhanced almost
linearly with increasing conductivity to a value between 6 and
7 S m−1 (4.5 wt% NaCl and 10 wt% Na2 SO4 , respectively).
Further increase in conductivity had no influence on the gas
formation rate for stable electrolytes. Gas formation seems
to further depend on the concentration of reactive electrolytes
as found for NH4 Cl since these electrolytes act as educts for
reactions initiated by discharge processes. As no dependence
of gas formation on pH values up to 13 was observed, it can
be concluded that water molecules rather than H+ or OH− are
the dominant precursors for H2 and O2 formation.
While most of the tested electrolytes could be used to
initiate discharges, this was not possible with nitrates of sodium
and potassium. It is not yet understood why these nitrates
7
J Schneider et al
prevent discharge initiation in particular when comparing with
experiments with HNO3 , where under similar experimental
conditions discharges could be initiated and significant gas
formation rates were measured.
The gas formation rate seems to be directly proportional
to RF power and proportional to the square of RF voltage.
The physical principles explaining the initiation of
discharges in the presented experimental setup under the
conditions defined here will be discussed in a forthcoming
publication [12].
In principle, potential applications of the phenomenon and
the novel reactor type can be seen in the field of ‘electrodeless’
water scission for hydrogen production and the decomposition
of water pollutants, in particular, of surfactants. However,
these applications compete with established techniques and
their practical use depends mainly on the energy efficiency.
Acknowledgment
The authors thank the graduate school BuildMoNa at the
Leipzig University for financial support of one of the
authors (JS).
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