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Journal of Electrostatics 96 (2018) 76–84

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Journal of Electrostatics
journal homepage: www.elsevier.com/locate/elstat

Efficacy of underwater AC diaphragm discharge in generation of reactive T


species in aqueous solutions
Anna Khlyustovaa,∗, Nikolay Sirotkina, Olga Evdokimovaa, Vadym Prysiazhnyib, Valery Titova
a
Laboratory of Chemistry of Hybrid Nanomaterials and Supermolecular Systems, G. A. Krestov Institute of Solution Chemistry of Russian Academy of Sciences,
Academicheskaja str., 1, 153045, Ivanovo, Russia
b
Institute of Physics and Biophysics, Faculty of Science, University of South Bohemia, Branisovska 1760, 37005, Ceske Budejovice, Czech Republic

A R T I C LE I N FO A B S T R A C T

Keywords: Underwater AC diaphragm discharge is energy efficient tool for decontamination of organic compounds from
Underwater diaphragm discharge aqueous solutions. This work is focused on the investigation of the electrical energy dissipation channels of the
Energy dissipation channels underwater AC diaphragm discharge and it chemical efficiency i.e. production of reactive species in aqueous
Reactive species solutions. Experimental results showed that more than 55% of total energy is consumed by heating of a solution
Energetic yields
and around 23% is used for the chemical reactions.

1. Introduction The chemical effect of underwater AC diaphragm discharge was


partially investigated. It was done by detecting the formation and ac-
Interaction of plasmas with liquids (either in contact or generated cumulation of the hydrogen peroxide [22]. The direct registration of
inside) leads to a wide range of chemical reactions. As a result of it, reactive species such as H•, OH•, hydrated electrons requires special
destruction of organic compounds, processes of synthesis and poly- equipment due to the short lifetime (10−9 s) [23–27]. The indirect
merization can be realized in systems built on the above-mentioned method of reactive species detection is based on the introduction of the
interaction [1–4]. Underwater discharge (realized in several config- scavenger that is trapping reactive species. Utilization of scavengers (or
urations) was suggested for several different applications such as sur- chemical probes) gives information about plasma generated reactive
face modification [5–8] or wastewater treatment [9–14]. The dia- species formation in liquid phase [28–40].
phragm discharge is one of the most investigated types of underwater Nowadays application of plasma discharge for biological systems
discharges [5–21]. The mechanisms of the underwater AC diaphragm (antibacterial/antimicrobial effects, toxicity to some cancer cells) is a
discharge and its physical and optical properties were investigated and hot topic [41–43]. And the role of reactive species or other factors in-
described elsewhere [5,13,15]. Its main advantage that makes it in- duced by electrical discharge in cell death is the open question. It was
teresting for applications is its relative simplicity of operation, i.e. ra- established that the input energy of electrical discharges in liquids is
ther expensive high voltage pulsed source is not required. consumed for acoustic waves, heating of solution, irradiation (including
The physical and optical properties of the diaphragm discharge have UV region), mechanical work, chemical processed etc. [44–48]. Present
been extensively studied already [5,12–19]. The efficiency of this dis- paper reports results of about energy dissipated channels and produc-
charge type was reported for sterilization [20], modification of natural tion of reactive species in aqueous solutions by underwater AC dia-
polymers [7], and the destruction of dyes [10,21–23]. These processes phragm discharge.
are induced by reactive species, such as H•, OH•, eaq −
, H2O2, which are
formed by activation and non-equilibrium dissociation of water mole- 2. Experimental section
cules. Information about reactive species concentration and their rate of
production assists in the optimization of a plasma process, resulting in The scheme of setup for generation of underwater AC diaphragm
better efficiency (in decontamination, synthesis or polymerization discharge is shown in Fig. 1. The graphite rods with diameter 5 mm
processes). However, the kinetics of reactive species formation by un- were used as the electrodes. The power supply for the excitation of the
derwater diaphragm discharge treatment was done for H2O2 only discharge consisted of a laboratory autotransformer and a high-voltage
[16–19]. step-up transformer. The power supply made it possible to ignite the


Corresponding author.
E-mail address: avlada5577@gmail.com (A. Khlyustova).

https://doi.org/10.1016/j.elstat.2018.10.002
Received 26 April 2018; Received in revised form 31 August 2018; Accepted 5 October 2018
0304-3886/ © 2018 Elsevier B.V. All rights reserved.
A. Khlyustova et al. Journal of Electrostatics 96 (2018) 76–84

Fig. 2. Typical voltage and current waveforms of underwater AC diaphragm


discharge. The active stage of discharge noted by pointers.

Fig. 1. Underwater AC diaphragm discharge scheme 1 – graphite electrodes, 2 – 3. Results and discussion
quartz ampoule, 3 – plasma zone.
3.1. Electrical characteristics of underwater AC diaphragm discharge
discharge at voltages up to 10 kV. The discharge was excited at different
voltages in the range 2–6 kV at alternating current varied from 20 to High current density (as a result of a small diaphragm size) results in
50 mA depending on the discharge burning regime. All experiments solution overheating and formation of the vapor bubble, which lead to a
were carried out in the non-symmetric H-type cell. In each experiment, break in the electrical circuit. The electromotive force (EMF) of the
a fixed solution volume of 170 mL was used. Two graphite electrodes voltage source and EMF of self-induction is applied to bubbles. The
were immersed into solution in separate parts of the cell. One of was development of a discharge occurs in bubbles. It leads to the collapse of
placed in a quartz ampoule with the hole (diaphragm) with the dia- the bubble with excitation of an acoustic wave (so-called “active
meter of 2 mm. The diaphragm discharge was initiated and propagated phase”). The current and voltage waveforms of the underwater AC
at the hole of the quartz ampoule in the bubble. The values of discharge diaphragm discharge are shown in Fig. 2. The burst of a bubble is ac-
current and voltage drop were recorded using the OWON PDS 5022C companied by the appearance of an additional peak on the current
digital oscilloscope and then processed on a computer. The voltage waveform with a lower current amplitude. This effect has 50 Hz fre-
divider was used to measure the voltage drop. The corresponding re- quency with 3 ms duration of the discharge active stage (pointed by
sistance values were 25 MΩ (R1) and 2.5 kΩ (R2). The temperature of arrows in Fig. 2). Therefore, the discharge operation can be referred to
the solution during the discharge treatment and after discharge off was as pulsed one excited by means of the AC source.
detected by chromel-alumel thermocouple monitored by digital multi- The average power is calculated by equation (1). It was decided to
meter RESANTA DT9208A. integrate over 30 seconds to obtain real value of the dissipated power
Solutions of K4[Fe(CN)6], KMnO4, and K2Cr2O7 were used as the (overcome stochastic discharge operation).
scavengers of OH• radicals, hydrated electrons, and hydrogen atoms, 1
t

respectively. The explanation of chemical processes of the reactive 〈P〉 =


T
∫ U (t ) i (t ) dt,
species and scavengers is described in Appendix in detail. The changes 0 (1)
of MnO4‾ ion concentration, the accumulation of [Fe(CN)6]3- ions and where U is voltage, i is current, and T is integration period (30 s).
CrV ions during the underwater AC diaphragm discharge treatment The average energy of discharge was calculated by:
were monitored by UV-vis absorption method. The samples (4 mL) were
t
drawn from solution at regular time intervals and absorbance was 1
measured at 525 nm (MnO4⁻), 420 nm ([Fe(CN)6]3-), and 350 nm (CrV)
〈Ed 〉 =
Td
∫ U (t ) i (t ) dt,
0 (2)
by UV-vis spectrophotometer (LEKI ss 2107, Russia).
Accumulation of H2O2, NO2‾ in solutions was determined by UV-Vis where Td is a total time of burning discharges. The average energy of
spectrophotometry at wavelength 407 nm and 540 nm, respectively. the one discharge is varied from 21 mJ to 189 mJ, which was de-
The concentration of NO3‾ ions was detected by nitrate selective elec- termined by current amplitude value.
trode. The total energy consumed in the plasma chemical cell was calcu-
The treatment time was 4 minutes. Short treatment time can be lated by equation (3)
explained as follows. In the case of the permanganate solution, MnO2 is Et = 〈P〉t, (3)
formed as a precipitate. The appearance of the dispersed phase in the
solution affects the absorbance spectra due to convection flows (at where < P > is average power and t is the experiment duration.
t > 5 min). Moreover, in the case of the ferrocyanide solution, the The discharge efficiency was calculated by equation (4)
appearance of the colloid phase of Prussian blue is detected after 5 min
〈Ed 〉⋅f
of treatment. In order to avoid these effects, the experimental time was η= ⋅100%,
〈P〉 (4)
limited.
The pH of the solutions before and after the discharge action was where < Ed > is average energy of discharge, < P > is average power,
measured by pH meter I-160 (Akvilon, Russia). and f is frequency of discharge appearance. Our calculations showed
that the efficiency of transferring power to the discharge is about 30%
of the total power delivered by the power supply.

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A. Khlyustova et al. Journal of Electrostatics 96 (2018) 76–84

Table 1
Energy balance in underwater diaphragm discharge.
Input energy Output

E = ∫ i(t)·U(t)dt 48 kJ Increase of solution temperature 27.73 ± 1.56 kJ


Fourier's heat losses 4.89 ± 0.5 kJ
Formation of gas bubble at 0.52 ± 0.04 kJ
diaphragm
Generation of acoustic waves 14.86
Radiant energy (UV-Vis radiation)
Initiation of chemical reactions

pressure shock wave. The pressure value is a function of breakdown


voltage and has a non-linear nature. Approximation data to our results
give a maximum pressure value of 10 bars. At these conditions, the
water/vapor density is decreased by 7%. Moreover, at this value of
pressure, the boiling point of water is increased till to 180 °C. It should
take into consideration in calculations. In the case of transient condi-
tions, the diameter of the bubble is dependent on time. Then the mass of
the bubble can be written as follows:
t 3
1 ⎛
Fig. 3. Kinetic curves of heating (1) and cooling-down (2) of the solution. m= πρ
6 ⎜
∫ d (t ) dt ⎞⎟ .
⎝ 0 ⎠ (8)
3.2. The energy dissipation channels in underwater AC diaphragm discharge For our calculations, the pre-breakdown condition was considered.
In this case, bubble diameter equals the diaphragm diameter
The acceleration processes in the liquid phase affected by under- (d = 2 mm) and its mass is calculated by using equation (7).
water discharge can be induced by conventional flows from the plasma Our calculation showed that more than 55% of the total energy used
zone and by increasing the solution temperature as a result of Joule to heat the solution (Table 1). Obtained results are in good agreement
heating. Thus, the total input energy may be consumed by solution with the data of works [44,45], which were obtained for underwater
heating and by the change of the system internal energy of the system spark discharge. It was found that 52–63% of energy can be spent on
(related to the heat of chemical reactions). During electrical discharge, water heating. The portion of input energy that distributed among a
the energy that dissipated into the solution led to an increase in thermal generation of the acoustic waves, radiant energy, and initiation of the
energy and conductive heat loss. chemical reaction in a solution is around 31%. Authors [45] established
To analyze the energy distribution channels in the discharge, the that around 39–45% of discharge energy is distributed among radia-
heating and cooling curves for the solution at the burning and after tion, chemical reactions, and ultrasonic waves. Unfortunately, we are
switching off the discharge were measured. The curves are shown in not able to measure radiant energy and acoustic energy. We can only
Fig. 3. analyze the published data. In Ref. [47] it was found that around 2% of
The thermal energy balance is written below [49]: electrical energy is converted into radiant energy. According to esti-
mations of Izdebski et al. [45] and Buogo et al. [46], 2.3–5.6% of input
c⋅m⋅(Tf − T0) = ∑ Ei + ∑ Ej, (5) energy can be transformed into the acoustic energy. Thus, around 23%
where с is the specific heat, m is the mass of the solution, Tf is final can be consumed by the initiation of the chemical reactions in a solu-
temperature of a solution, T0 is initial temperature of solution, ∑Ei is the tion.
energy of the heat sources, ∑Ej is the energy of the heat losses.
The quantitative value of the solution temperature increase can be 4. Kinetics of reactive species
estimated by the curve of heating. The heat losses can be found in the
initial part of cooling curve. 4.1. Pathways of reactions
The energy required for the formation of a gas bubble at the dia-
phragm can be estimated by: The reactive species are formed by non-equilibrium dissociation of
water molecules
Eb = Q⋅N = (Qh + Q v ) N = (c⋅mb (Tbp − Ts ) + r⋅mb) N , (6)

H2 O → H2 O∗ → H·, OH·, eaq (9)
where N is the number of microdischarges per second, Qh and Qv are
the energy for temperature raise and the energy for water vaporization, These primary reactive species react with each other inducing for-
mb is the mass of formed bubble, Tbp is the boiling point of water, Ts is mation of another reactive species and more stable compounds, such as
the average temperature of the solution, r is the specific heat of va- hydrogen peroxide. Principal chemical processes involving reactive
porization. species inside plasma in aqueous solutions were described in Refs.
The mass of the bubble is estimated as: [34,51]. In the presence of scavenger, the main reaction will be the
reaction of trapping of reactive species.
4 d 3 1
m w = ρ⋅V = ρ π ⎛ ⎞ = πρd3, Measurements of pH of the solutions after discharge action did not
3 ⎝2⎠ 6 (7) show significant changes in pH values ( ± 0.2 unit). It means that we
where ρ is water vapor density, d is a bubble diameter. can do some simplifications on our kinetic schemes.
It is known that water density depends on pressure. Authors [50]
experimentally studied the development of an electrical discharge in 4.2. MnO4⁻ ion
water. An electrical discharge propagates in gas bubbles, which formed
close to local heating points in liquid. The breakdown of the electrical In the case of potassium permanganate solution, the following re-
circuit by the gas bubble induces the generation of a high amplitude actions of reactive species with permanganate ion could occur in liquid

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A. Khlyustova et al. Journal of Electrostatics 96 (2018) 76–84

(reaction rate constants are given from Refs. [52,53] at T = 293 K): O2− + [Fe (CN )6]3 − → [Fe (CN )6]4 − + O2 k = 9 × 102M−1s−1

eaq + MnO4− → MnO2 + 2O− k = 3.3 × 1010M−1s−1 (23)
(10)
H2 O2 + 2[Fe (CN )6]4 − → 2[Fe (CN )6]3 − + 2OH− (24)
MnO4− + H • → MnO42 − + H+ k = 3.3 × 1010M−1s−1 (11)
According to our previous data, experiments with ferrocyanide so-
MnO4− + O2− → MnO42 − + O2 k = 8 × 106M−1s−1 (12) lutions did not result in the formation of the hydrogen peroxide [30].
However, there are other pathways to produce H2O2. According to
2MnO4− + 5H2 O2 + 6H+ → 2Mn2 + + 8H2 O + 5O2 (13)
[56], thermal oxidation of ferrocyanide ions by hydrogen peroxide is
It should be noted that the high value of the rate constant for re- very slow in solutions. This reaction takes more than 4 hours. There-
action (11) was obtained in an acid solution (pH = 2) [53]. However, fore, the interaction between [Fe(CN)6]4- ion and H2O2 does not occur.
the contribution of this reaction in reducing the permanganate ion was Interaction of hydrogen atoms with ferricyanide ions leads to the for-
considered. To minimize reduction processes induced by hydrated mation of aquapentacyanoferrate (II) ion (reaction (21)), which has
electrons in H• atoms and OH• radicals detection experiments, several optical absorption at 480 nm [57]. The peak appearance at 480 nm was
experiments were conducted with the flow of N2O through the solution not detected during underwater AC diaphragm discharge. Reaction (22)
(resulted in bubbling). Nitrous oxide is known as the scavenger of the could take place in acid medium and reaction (23) can proceed in alkali
hydrated electrons [54] (reaction 14). The reaction rate for interaction medium, where radical pair HO2•/O2¯ has a pH depended equilibrium
between the H• atom with nitrous oxide is lower than that for reaction [58]. Moreover, the rate constants of reactions (22) and (23) are very
(14) by a factor of 103 [53,54]. low implying that they cannot compete with the much faster reaction
− (20) and ensure that hydroxyl interacts primarily with ferrocyanide
N2 O + eaq → N2 + OH· + OH− k = 9.1 × 109M−1s−1 (14) ions (oxidation mechanism) if similar concentrations of HO2• and OH•
In this case, the reducing process of MnO4‾ ions proceeds through are presented.
the following solution color changes: purple, green, red and brown It should be noted that the concentration of the reactive species in
precipitate appearance. The consequent reactions are: solution is non-uniform. Concentration is higher in the near plasma
regions and negligible in the solution bulk. Thus, all kinetic schemes are
MnVII→MnVI→MnV→MnIV (as MnO2)→Mn2+ (15) described in areas that are near the plasma zone. Applying the sta-
The appearance of MnO2 was observed after 55 minutes of dis- tionary state approximation to these radicals, we have:
− −
charge treatment with N2O. Note that the formation of MnO2 occurred g (eaq ) − k10 [eaq ][MnO4−] − Σki [eaq

][Ci] = 0 (25)
after the first minute of treatment without N2O bubbling. Hence, the
main trapping pathway for hydrated electrons is reaction with the g (H •) − k17 [H •][Cr2 O72 −] − Σki [H •][C i] =0 (26)
MnO4¯ ion in the neutral medium (reaction 10). The appearance of
Mn2+ ion in the solution is accompanied by decolorization of the so- g (OH •) − k20 [OH •][[Fe (CN )6]4 − ] − Σki [OH •][Ci] = 0, (27)
lution at a long time of treatment (t > 5 min). whence
− −
4.3. Cr2 O72 − ion g (eaq ) = k10 [eaq ][MnO4−] + ∑ ki [eaq− ][Ci] (28)

g (H •) = k17 [H •][Cr2 O72 −] + Σki [H •][Ci] (29)


In neutral solutions of potassium dichromate, the conversion of
Cr2 O72 − ion to CrO42 − takes place (reaction (16)) (reaction rate constant g (OH •) k20 [OH •][[Fe (CN )6]4 − ] [OH •][C
= + Σki i] (30)
is given from Ref. [55]).
Kinetic curves of reduction and oxidation processes in the solutions
Cr2 O72 − + H2 O → 2CrO42 − + 2H+ k = 4.2 × 1014M−1s−1 (16) during the underwater diaphragm discharge treatment are presented in
In the presence of nitrous oxide, the reactions can be written as Fig. 4. The kinetics of reducing of MnO4‾ ions to MnO2 (Fig. 4a) is
follows. described by the pseudo-first-order equation (with correlation coeffi-
cients (R2) of 0.97–0.98): C = C0 exp(−Kt ) , where C0 – is the initial
CrO42 − + H • → HCrO42 − k = 2.2 × 1010M−1s−1 (17) −
concentration of ions, K = k10[eaq ] is the observed rate constant. It al-
lows to estimate the steady-state concentration of hydrated electrons
2CrO42 − + H2 O2 → 2CrO43 − + O2 + 2H+ k = 26M−1s−1 (18)
(see Table 2). The dependence of the ferricyanide ions accumulation on
CrO43 − + OH • → CrO42 − + OH− k = 1.5 × 109M−1s−1 (19) the treatment time had nonlinear behavior at I > 45 mA (Fig. 4b). The
appearance of leveling values means that the rate of formation is
It is possible that reaction (18) in neutral solution is unlikely at the equaled to the rate of consumption (transformation to Prussian blue).
initial time of discharge treatment because its rate constant is rather Therefore, the initial part of a kinetic curve of accumulation used to
low and the amount of hydrogen peroxide in the solution is not suffi- estimate the initial rate of oxidation process (ferricyanide ions forma-
ciently high. We suggested that at time t→0 the concentration of CrO43 − tion). The ferricyanide formation rate (oxidation process) is given by:
is very low and the reaction (19) can be neglected.
d [[Fe (CN )6]3 − ]
= k20 [OH •][[Fe (CN )6]4 − ] = υ,
4.4. [Fe (CN )6]4 − ion dt (31)
The hydroxyl radical concentration can be expressed by equation
In the case of the ferrocyanide solution bubbled with N2O, the fol- (31). The obtained results are presented in Table 2.
lowing reactions can take place:
υ
[OH •] =
OH • + [Fe (CN )6]4 − → [Fe (CN )6]3 − + OH− k = 1.05 × 1010M−1s−1 k20 [[Fe (CN )6]4 − ] (32)
(20) V
In spite of Cr transient formation between Cr and Cr , the 6+ 3+

H • + [Fe (CN )6]3 − → Fe (CN )5 H2 O3 − + HCN k = 6.0 × 109M−1s−1 curves of CrV ion accumulation had saturation (Fig. 4c). If the transition
(21) of Cr6+ to CrV and then to Cr3+ takes place, the curve of accumulation
would have a maximum. The conditions of our experiments allow ob-
HO2• + [Fe (CN )6]4 − → [Fe (CN )6]3 − + HO2− k=1× 10 4M−1s−1 taining the CrV as the final product (neutral pH, low concentration of
(22) potassium dichromate, low discharge currents). The kinetic scheme for

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A. Khlyustova et al. Journal of Electrostatics 96 (2018) 76–84

Then the equation for [H•] can express via the initial rate formation:
υ
[H •] = .
k17 [Cr2 O72 −] (34)
V
The initial rates of Cr formation were estimated by the initial parts
of kinetic curves accumulation, which are presented in Table 2.
The production rates for reactive species are calculated by using
equations (28-34). Fig. 5 shows the production rates of reactive species
for various discharge currents. Our results showed that rates of gen-
eration of reactive species are different. We assumed that the increase
of the production rates for reactive species with increasing of a dis-
charge current (input energy) is more pronounced. However, the pro-
duction rate for hydrogen atoms is about 7 × 10−7 M/s and do not
depend on the discharge current for our experimental conditions. It
means that the contribution of ∑ki[H•][Ci] term in Eq. (29) is increased.
This term includes all interaction between H• atoms and other reactive
species in solution. And reactions between hydrogen atoms and hy-
droxyl radicals and hydrated electrons are the main ways for the dis-
appearance of H• atoms by increasing input power at our experimental
conditions.
According to reaction (9), one can suggest that the number of H•
radicals, hydrated electrons, and OH• radicals will be the same within
processes of activation and non-equilibrium dissociation of water mo-
lecules. However, our obtained results are contradicted by this sug-
gestion. On the other hand, this reaction is the scheme of the activation
process. According to data of radiation chemistry, the breaking H-OH
bond results in yielding of the mixture of the radical and molecular
species [53].

H2 O → H2 O∗ → 0.028OH·+0. 27eaq + 0.06H·+0.05H2 + 0.07H2 O2
+ 0.27H3 O+ (35)

It means that the concentration of hydrogen atoms is less than the


concentration of hydroxyl radicals and hydrated electrons at high input
energy. On the other hand, the results of numerical simulation of the
kinetics of the reactive species in gas and liquid phases showed that
concentration of H• atoms and OH• radicals can differ in 6 order of the
magnitude [59]. We suppose that it can be connected with the set of
chemical reactions with hydrogen atoms which included (or not) in
kinetic models because hydrogen atoms are not the main reactive
species (such as hydroxyl radicals).

4.5. Long-lived reactive species

The reactive nitrogen species did not register in all experiments with
underwater diaphragm discharge. It is not unexpected because the
plasma zone has no contact with air. In the case of H2O2, it should be
noted that hydrogen peroxide is not detected in experiments in pre-
sence of ferrocyanide ions (as the scavenger of OH• radical). In other
experiments, without OH radical scavengers, the accumulation of hy-
drogen peroxide in solution during the plasma treatment was registered
(Fig. 6). Experimental results showed that values of concentration are
lower in comparison with tubular discharge (9 mM) [60] and under-
water capillary discharge (7.5–15.6 mM) [17,18,61].

4.6. Yields of reactive species

To compare the efficiency of reactive species production by dif-


Fig. 4. Kinetic curves of MnO4⁻ ions (a), [Fe(CN)6]3- ions (b) and CrV ions (c) in ferent discharge types, the experimental conditions (discharge power,
solution during underwater AC diaphragm discharge treatment. solution volume, etc.) should be taken into consideration. We strongly
believe that energetic yield (G) is more appropriate for efficiency
CrV ion formation in solution is written as follow: comparison. The equation for the calculation of the energetic yield of
reactive species is:
d [Cr V ]
= k17 [H •][Cr2 O72 −] = υ gNA Ve
dt (33) G= × 100 molecules/100 eV,
〈P〉 (36)

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Table 2
Steady state concentrations and rates of oxidation and reduction processes by underwater AC diaphragm discharge treatment.
I, mA KMnO4 solution K4[Fe(CN)6] solution K2Cr2O7 solution

−14 −7 • −14

[eaq ]ss, 10 M υ, 10 M/s [OH ]ss, 10 M υ, 10−7 M/s [H•]ss, 10−14 M

20 1.24 ± 0.18 5.96 ± 0.61 5.42 ± 0.50


25 2.39 ± 0.27 6.13 ± 0.63 5.57 ± 0.52
30 2.42 ± 0.24 3.71 ± 0.31 3.53 ± 0.20 6.25 ± 0.65 5.68 ± 0.52
35 2.7 ± 0.2 5.67 ± 0.48 5.40 ± 0.30 6.27 ± 0.65 5.70 ± 0.54
40 3. 45 ± 0.39 7.19 ± 0.65 6.85 ± 0.42 6.32 ± 0.62 5.75 ± 0.56
45 3.7 ± 0.58 9.92 ± 0.84 9.45 ± 0.71 6.33 ± 0.62 5.75 ± 0.56
50 3.88 ± 0.82 13.25 ± 0.86 12.61 ± 0.96 6.35 ± 0.64 5.77 ± 0.58

Table 3
Energy yields (molecules/100 eV) of reactive species in aqueous solutions by
electrical discharge treatment.
Experimental conditions (discharge type, G value (molecule/ Ref.
gas, scavenger) 100 eV)

Hydrated electrons
Glow discharge electrolysis, hydrogen, 0.016 [32]
monochloroacetic acid
Silent discharge, argon, K3[Fe(CN)6]+NaN3 0.06 [33]
Atmospheric pressure glow discharge, air, 0.13 [35]
KMnO4
Underwater AC diaphragm discharge, 0.07 This work
KMnO4
Hydrogen atoms
Silent discharge, Ar, He, Ce(SO4)2 0.6–1.2 [37–39]
Contact glow discharge, air, maleic acid 0.05–0.08 [40]
Underwater AC diaphragm discharge, 0.06 This work
K2Cr2O7
Hydroxyl radicals
Pulsed tubular discharge, Ar, ethanol, 3–5 [29]
TiOSO4
Atmospheric pressure glow discharge, air, 0.17 [30]
K4[Fe(CN)6]
Pulsed corona, air, phenol 0.06 [62]
Fig. 5. Reactive species production rates versus discharge current. Pulsed corona, terephtalic acid, 0.01 [63]
dimethylsulfoxide
Underwater AC diaphragm discharge, K4[Fe 0.03 This work
(CN)6
Hydrogen Peroxide
Underwater DC capillary discharge 0.08 [19]
Pulsed corona in water 0.047–0.091 [63]
Underwater capillary discharge 0.016 [61]
Underwater AC diaphragm discharge 1.06 This work

showed that the yields of reactive species do not depend on the dis-
charge current. The average values are presented in Table 3.
It is difficult to compare the G values obtained by the action of
underwater discharges and discharges above liquids due to different set
reactions in the kinetic schemes. But we can compare the efficacy of our
type of the underwater discharge with other underwater discharge
plasmas. To our knowledge, there is no data on generation rates for
hydrated electrons and H• atoms by underwater discharges. and we can

compare with published data for discharges above liquids. The G(eaq )
value has the same order of the magnitude with values of yield by silent
discharge and glow discharge electrolysis [32,33]. The value of yield
for H• atoms is compared with data obtained by DC contact glow dis-
charge [40].
Regarding hydroxyl radicals, one of the reasons for the difference of
Fig. 6. Accumulation of hydrogen peroxide in solutions during underwater
our G value may be explained by using the various scavengers (see
diaphragm discharge treatment in presence of MnO4⁻ ions (1) and Cr2O72− ions
(2) at discharge current of 50 mA. Table 3). The highest value of the OH• radical energy yield of was found
for a pulsed tubular discharge with liquid film in argon (3–5 molecules/
100 eV) [29] which obtained from the H2O2 formation (detected by
where g is the production rate (M/s), NA is Avogadro's number TiOSO4).
(6.02 × 1023 particles/mole), V is the solution volume (0.17 L), e is Regarding hydrogen peroxide, our calculation showed that the en-
charge of electron (1.6 × 10−19 C), < P > is average power of dis- ergetic yield of hydrogen peroxide is higher than for pulsed corona
charge (W) (calculated from eq. (2)). The results of our calculations discharge in water, dielectric barrier discharge in direct contact with

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A. Khlyustova et al. Journal of Electrostatics 96 (2018) 76–84

water and underwater DC diaphragm discharge [19,61,63]. It is ex- 5. Conclusions


plained that the high value of the energetic yield is calculated by di-
viding production rate by power. In our experiments, the input power is The reactive species originating from aqueous solution by under-
less in compared to underwater capillary discharge [61]. water AC diaphragm discharge were quantified using the scavengers.
It is known that the energy for water bond dissociation (H-O-H) into The efficacy of this type of discharge was described by estimations of
O-H and H is 498 kJ/mol [64]. Our calculations showed that 23% of the energy dissipated channels and energetic yields of the reactive
input energy (around 11 kJ) can be consumed by the initiation of species. Although we obtained low energetic yields for the reactive
chemical reactions. It means that this energy is enough for the dis- species (H•, OH•, hydrated electrons) due to a small part of input energy
sociation of 0.4 g of water (0.24% of total volume). It may explain the that spent for initiation of the chemical reactions, our results showed
low yield of the reactive species in comparison with other types of that we have the more suitable conditions for production and accu-
plasmas with liquid (Table 3). On the other hand, the more than 55% of mulation of H2O2.
total energy is spent on heating of solution. The temperature rise leads
to increasing of rates of the chemical reactions. And consequence, the Acknowledgments
yield of H2O2 is high.
From point of view of the generation of the short-lived reactive Authors would like to thank Dr. Ludmila Kuz'micheva for helpful
species (H•, OH•, hydrated electrons), the other types of electrical dis- discussion on the chemistry of potassium dichromate, Mr. Aleksey
charge plasma are more effective than our type of underwater dis- Ganin for performing the energy estimations.
charge. On the other hand, the production of hydrogen peroxide is more This research did not receive any specific grant from funding
energy efficacy by the underwater AC diaphragm discharge. agencies in the public, commercial, or not-for-profit sectors.

Appendix

The oxidation of the potassium ferrocyanide has been successfully used as a dosimeter for OH radicals [30,65]. The use of salicylate ion and
phenol as scavengers of hydroxyl radicals were described in previous works [34,62,66–69]. However, using these compounds for trapping OH•
radicals in solution at pH∼7 requires specific conditions to prevent reduction processes [34,70]. The MnO4‾ ion was used as the scavenger of
hydrated electrons in Ref. [35]. Potassium dichromate solution was chosen as the scavenger for H• atoms. For instance, some works report about
investigations of the reduction kinetics of CrVI to CrIII by various types of gas discharges [51,71–73]. It was noted that in acid and alkali solutions the
reducing CrVI occurs to CrIII through the formation of transient forms of Cr. In acid solution, the reducing process induces by hydrogen atoms
whereas, in alkali solutions, CrVI reduced by hydrated electrons. In a neutral solution, the reducing process can be more complicated owing to the
presence of both H• atoms and hydrated electrons. In spite of this, the dichromate ion can be used as a scavenger of H• atoms.
Kalkar et al. [74] demonstrated that the concentration of permanganate ion greater than 0.4 mM is sufficient to remove all hydrated electrons in a
liquid medium. In the case of OH• radical detection, Gupta and Bluhm [75] established that in order to successfully compete with radical re-
combination (formation of H2O2), 6 mM chemical probe concentration is enough.
The solutions with 0.5 mM of KMnO4 (pH 6.5, conductivity 35 μS/cm) and 0.5 mM of K2Cr2O7 (pH 6.5, conductivity 60 μS/cm) were used as the
scavengers of reductive reactive species. The solution of 1 mM of K4[Fe(CN)6] (pH 7, conductivity 640 μS/cm) was used as the scavenger of hydroxyl
radical. The larger value of ferrocyanide ion concentration is explained by low values of the extinction coefficient of ferricyanide ion in the maximum
of the absorption band (ε = 505 M−1cm−1 at 420 nm) compared with MnO4‾ ion (ε = 2500 M−1cm−1 at 525 nm) and CrV ion (ε = 3150 M−1 cm−1
at 350 nm) [76]. The untreated K2Cr2O7 solution has a maximum absorbance at 360 nm. The appearance of CrV ion in solution leads to a blue shift
and peak appearance at 350 nm (see Fig. A1) [77,78].

Fig. A1. Absorbance spectra of untreated (1) and after 60 s treatment by underwater AC diaphragm discharge (2) of K2Cr2O7 solution.
Hydrogen peroxide accumulation by electrical discharge treatment under various experimental conditions has previously been reported [79]. It
was found that reduction of permanganate ions by hydrogen peroxide in acid solution is thermodynamically favorable since the standard electrode
potential is +1.51 V for MnO4‾ reduction. This potential value is higher than the standard electrode potential for H2O2 oxidation (−0.682 V). The
reduction mechanism of MnO4‾ by H2O2 was described in Ref. [79]. In acid solution, the hydrogen peroxide leads to a direct formation of Mn2+ by

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A. Khlyustova et al. Journal of Electrostatics 96 (2018) 76–84

reaction (12). Upadhaya and co-workers [80] found that H2O2 reduced only 10% of the permanganate ions. The possibility of reducing reaction with
the participation of H2O2 at pH∼7 was considered in our experiments also. Several experiments on the study of the reduction process of MnO4‾ by
hydrogen peroxide were carried out. The H2O2 was added to the solution (c(H2O2) = 10 mM) without diaphragm discharge ignition. The absorbance
spectroscopy results showed that reducing process is very slow (more than 3 hours). The maximum of absorbance peak shifted on 5 nm in the
shortwave region. It indicates that the MnV ions appeared (as H3MnO4) in solution (reaction (A1)).
KMnO4 + H2 O2 + H2 O → H3 MnO4 + O2 + KOH (A1)
A shift of the absorbance peak by the underwater AC diaphragm discharge treatment was not detected. This indicates that the reducing process of
MnO4‾ ion by hydrogen peroxide did not occur in a neutral solution.
The reduction of MnO4‾ ions by dissolved oxygen in neutral solution is thermodynamically unfavorable because the standard electrode potentials
for MnO4‾ reduction and for O2 oxidation are +0.6 V (pH 7) and +0.815 V (pH 7), respectively.

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