Ultrasonics Sonochemistry: Elodie Dalodière, Matthieu Virot, Philippe Moisy, Sergey I. Nikitenko

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Ultrasonics Sonochemistry 29 (2016) 198204

Contents lists available at ScienceDirect

Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Effect of ultrasonic frequency on H2O2 sonochemical formation rate


in aqueous nitric acid solutions in the presence of oxygen
Elodie Dalodire a, Matthieu Virot a,, Philippe Moisy b, Sergey I. Nikitenko a
a
b

Institut de Chimie Sparative de Marcoule, ICSM-UMR5257 CNRS/CEA/UM2/ENCSM, BP17171, F-30207 Bagnols sur Cze, France
CEA, Nuclear Energy Division, RadioChemistry & Processes Department, BP17171, F-30207 Bagnols sur Cze, France

a r t i c l e

i n f o

Article history:
Received 29 May 2015
Received in revised form 14 September
2015
Accepted 22 September 2015
Available online 25 September 2015
Keywords:
Sonochemistry
Ultrasound
Nitric acid
Nitrous acid
Hydrogen peroxide
O2

a b s t r a c t
The influence of the ultrasonic frequency (20 kHz, 207 kHz, and 615 kHz) towards the formation kinetics
of H2O2 under Ar and Ar/(20 vol.%)O2 atmospheres was evaluated in pure water and aqueous nitric
solutions. Results obtained at low frequency ultrasound demonstrate that hydrogen peroxide formation
is enhanced under an Ar/O2 gas mixture whatever the sonicated medium. Nevertheless, H2O2 yields are
higher in aqueous nitric solutions whatever the nature of the saturating gas. These observations are consistent at high frequency ultrasound under Ar gas notwithstanding higher yields for H2O2. Surprisingly,
an inverse tendency is observed for high frequency sonolysis carried out under an Ar/O2 atmosphere:
higher yields of H2O2 are measured in pure water. Further studies in the presence of pure Ar revealed
a more important decomposition of nitric acid under high frequency ultrasound leading to higher yields
of both HNO2 in the liquid phase and NO in the gas phase. In the presence of Ar/O2 mixture, the intrabubble oxidation of NO causes cavitation bubble depletion in O2 leading to the drop of H2O2 yield. On the
other hand, it was found that for Ar/(20 vol.%)O2 mixture there is no influence of oxygen on HNO2 yield
whatever the ultrasonic frequency; this is most likely explained by two processes: (i) HNO2 formation
results from nitrate-ion thermolysis in the liquid reaction zone surrounding the cavitation bubble, and
(ii) effective intrabubble oxidation of NOx species by oxygen to nitrate-ion.
2015 Elsevier B.V. All rights reserved.

1. Introduction

under argon can be significantly enhanced when increasing the


ultrasound frequency [1115] or the acoustic power [14,15].

Sonochemical reactions in nitric acid solutions have attracted


considerable attention as a potentially reagent-free route to
control the oxidation states of actinide ions during spent nuclear
fuel reprocessing mostly due to the in situ generation of hydrogen
peroxide and nitrous acid [1]. In pure water saturated with noble
gases, power ultrasound causes the homolytic splitting of H2O
molecules yielding H and OH radicals (reaction (1)) [26]. These
highly reactive species mostly recombine into H2O inside the cavitation bubble [5,6]. Some of OH radicals (roughly 20% [6,7]) can
nevertheless diffuse to the bubble interface where the temperatures are lower, and recombine into hydrogen peroxide (reaction
(2)). Molecular hydrogen H2 is formed as a recombination product
of H radicals mostly in the gaseous phase of the collapsing bubble
(reaction (3)) [5,8]. Several investigations devoted to the kinetics of
H2O2 sonochemical formation have been reported in the literature
[912]. It was showed that the H2O2 formation rate in pure water

H2 O ! ! H OH

2OH ! H2 O2

2H ! H2

Corresponding author.
E-mail address: matthieu.virot@cea.fr (M. Virot).
http://dx.doi.org/10.1016/j.ultsonch.2015.09.014
1350-4177/ 2015 Elsevier B.V. All rights reserved.

Sonication of aqueous nitric acid solutions is known to initiate


the formation of nitrous acid in solution and NOx species that
can be observed in the gaseous phase (reaction (4)) [16]. In 4 M
HNO3 solution sonicated at 20 kHz under Ar bubbling, HNO2 production was shown to accumulate linearly versus time during
the first 60 min of sonolysis [17]. After 180 min, a HNO2 steadystate concentration is then observed. This steady-state is related
to the sonochemical degradation of HNO2 and the subsequent
release of NO and NO2 into the outlet gas (reaction (5)) [17,18].
At moderate concentration of HNO3 (<4 M), HNO2 is principally
formed as a result of NO
3 ion thermolysis at the interfacial bubble/solution region (reaction (6)) [1,19]. In more concentrated
solutions, its formation can also result from HNO3 molecule degradation inside the bubble followed by secondary reactions with NOx

E. Dalodire et al. / Ultrasonics Sonochemistry 29 (2016) 198204

in the bulk solution (reactions (7)(9)) [1]. Note that nitrates and
nitrites can also be formed in pure water saturated with air or
N2/O2 gas mixture [15].

2HNO3 ! ! 2NO2 H2 O 1=2O2

2HNO2 ! ! NO NO2 H2 O

H NO3 ! ! HNO2 1=2O2

2NO HNO3 H2 O ! 3HNO2

2NO2 $ N2 O4

N2 O4 H2 O ! HNO2 HNO3

Reactions (4) and (5) may occur inside the bubble, the
decomposition of HNO2 and HNO3 in such extreme conditions
can be rapid. Kinetic for reaction (6) is supposed to be lower and
probably depends on the interface temperature. In these
conditions, a higher decomposition rate can be assumed at higher
ultrasonic frequencies. Presuming a NO steady state in the gas
phase, the kinetic constant for reaction (7) is k(7) = 0.7 L3 mol3 s1
[18]. The kinetic constants for NO2 dimerization (reaction (8)) and
for N2O4 disproportionation at 298 K (reaction (9)) are respectively
k(8) = 4.5  108 L mol1 s1 and k(9) = 1.7  1010 L mol1 s1 [18].
In sonicated nitric solutions, hydrogen peroxide cannot
accumulate due to its rapid reaction with nitrous acid according
to the reaction (10) [17]. However, in the presence of anti-nitrous
reagents such as hydrazinium nitrate or sulfamic acid which scavenge HNO2 by the reaction (11) and (12), H2O2 can accumulate at
a higher rate than that observed in pure water [20,21]. This
phenomenon is attributed to the reaction of nitrate ions with OH
radicals forming NO3 radical species, which, after hydrolysis, yield
hydrogen peroxide in solution (reactions (13) and (14)). In this
mechanism, only one hydroxyl radical is used whereas two are used
in pure water to generate one molecule of hydrogen peroxide.

HNO2 H2 O2 ! HNO3 H2 O

10

N2 H5 2HNO2 ! N2 O N2 3H2 O H

11

HNO2 NH2 SO3 H ! N2 H2 O H2 SO4

12

NO3 H OH ! NO3 H2 O

13

NO3 H2 O ! NO2 H2 O2

14

In water, the sonochemical yield of H2O2 can be increased in the


presence of oxygen. Several authors have reported higher H2O2
yield for Ar/(2030 vol.%)O2 gas mixtures. This was attributed to
much more significant generation of both OH and HO2 radicals
[12,21,22]. According to these observations, one can assume that
the sonication of a correctly tuned system combining nitric acid
(in the presence of anti-nitrous reagent) and Ar/O2 atmosphere
may enhance H2O2 yields. To the best of our knowledge, the study
at such condition has never been reported in the literature. Furthermore, the sonolysis of nitric acid has been only studied under
low-frequency ultrasound (20 kHz). The aim of the present work
is to investigate the behavior of aqueous nitric solutions in the
presence of Ar/O2 gas mixtures at different ultrasonic frequencies.
2. Experimentals
2.1. Materials
Reagents used in this study were all of analytical grade and
were purchased from Sigma Aldrich and VWR. To prepare aqueous

199

solutions for experiments, purified ultrapure water having a resistivity higher than 18.2 MO cm at 25 C was used. The experiments
were performed under pure Ar (purity >99.9%) or with an Ar/O2
(20 vol.% of O2) mixture provided by Air Liquide. For several
experiments, hydrazinium nitrate [N2H5NO3] (NH) or sulfamic acid
NH2SO3H were used as anti-nitrous reagent. NH was prepared by
careful neutralization of hydrazine hydrate with HNO3.
2.2. Sonochemical experiments
Experiments at low frequency ultrasound (20 kHz) were
performed with a 1 cm2 titanium horn fitted on top of a 50 mL
homemade reactor. The power supply was provided by a 750 W
generator (sonics & materials vibracell VCX 750). High frequency
studies (207 and 615 kHz) were performed in a 250 mL cylindrical
reactor mounted on top of a 25 cm2 high-frequency transducer (L3
communications ELAC Nautik) connected to a 125 W generator
(LVG 60 RF-generator). For high frequency experiments, the solution was stirred in the meantime at 240 rpm to obtain a homogeneous system. Both reactors are tight and are supplied with several
connections dedicated to temperature control, solution sampling,
gas bubbling, and a connection to a mass spectrometer. In order
to compare accurately the experimental results, the acoustic power
P (W) delivered to the solution was determined by the calorimetric
method (reaction (15)). This was then used to determine the
specific acoustic power Pac expressed in W mL1 (reaction (16)).

PW mC p

Pac

 
dT
dt 0

PW
V mL

15

16

where, m is the mass of water (kg), Cp, is the calorific capacity


of the water at room temperature and atmospheric pressure
(4.18 kJ kg1 K1), (dT/dt)0, is the initial rate of water heating during
sonication, and V is the volume of the sonicated solution (mL).
During sonication, the temperature was maintained at 21 1 C
with a Huber CC1 cryostat and was controlled with a thermocouple
immersed in the reactor. Various treated solutions were sparged
with gas (constant rate flow: 100 mL min1) 15 min before starting
ultrasound which was then maintained into the solution during
the whole experiments. All materials constituting the sonoreactor
(horn, tube for gas bubbling, thermocouple) were placed
reproducibly in the solution to avoid artefacts.
2.3. UVVis spectroscopy
During sonolysis, aliquots of solutions (1 mL) were sampled
with a syringe through a septum and filtered with 0.2 lm PTFE filters. Then, samples were diluted with appropriate solutions before
analysis with UVVis absorption spectrophotometry (Thermo
Evolution 220). Absorption spectra were recorded from 300 to
750 nm. The formation of H2O2 was followed by mixing the sampled solution (1:1) with 1.2  102 M TiOSO4 (0.330 g TiOSO4 dissolved in 100 mL of pure water under stirring and previously
gently heated in 3.5 mL of 18 M H2SO4) to form a colorimetric complex absorbing at 410 nm (e = 698 cm1 M1). A calibration curve
was previously prepared with a standard H2O2 solution.
The formation of HNO2 during sonolysis of aqueous nitric solutions was followed by UVVis absorption spectrophotometry using
the Griess method, which consists to the measurement of a colorimetric complex formed by the reaction of NO
2 with sulfanilic acid
and a-naphtylamine (k = 535 nm, e = 41,500 cm1 M1). The procedure consists of mixing filtered solution aliquots (0.11 mL) with
2 M NaOH (1 mL), sulfanilic acid (3.45  102 M, 0.6 g sulfanilic

200

E. Dalodire et al. / Ultrasonics Sonochemistry 29 (2016) 198204

acid in 20 mL of concentrated HNO3 diluted in 100 mL pure water,


1 mL), a-naphtylamine (4.19  102 M, 0.6 g dissolved in 5 mL HCl
diluted in 100 mL pure water, 3 mL), and completed to 10 mL with
a buffer solution of 0.8 M sodium acetate and 3.2 M chloroacetic
acid (54.4 g CH3COONa and 151.2 g CH2Cl-COOH dissolved in
500 mL of pure water). A calibration curve was previously prepared
with sodium nitrite solutions. To calculate the specie formation
rates, the linear part of the curve obtained during the first 60 min
was used and was expressed as W0(H2O2) or W0(HNO2) for hydrogen peroxide and nitrous acid, respectively. In order to compare
accurately the results obtained at various frequencies and various
acoustic powers for H2O2, the energetic yield G (expressed in
mol kJ1) was used (reaction (17)). The statistical error for H2O2
and HNO2 formation rates are estimated to be about 10%.

W 0 H2 O2
60Pac

17

2.4. Mass spectrometry


Gaseous products formed during sonolysis (NO, NO2) were followed qualitatively with a quadrupole mass spectrometer (Prolab
300, Thermo Fischer). Prior to analyses, the water vapor present in
the outlet gas was trapped with molecular sieves (Sigma Aldrich, 3 ).

Table 1
Hydrogen peroxide formation rates (W0(H2O2), lM min1) measured during sonolysis
of H2O and 1 M HNO3 (in the presence of 0.1 M NH) under Ar and Ar/O2 as a function
of the applied ultrasonic frequency (T = 21 C).
W0(H2O2) in lM min1
f (kHz)

20
207
615
615

Pac (W mL

0.37
0.16
0.17
0.21

1

H2O

1 M HNO3/0.1 M NH

Ar

Ar/O2

Ar

Ar/O2

1.1 0.1
2.1 0.2
2.6 0.3
3.8 0.4

2.8 0.3
14.6 1.5
14.3 1.4
19.6 2.0

2.5 0.3
4.3 0.4
4.7 0.5
6.0 0.6

3.9 0.4
10.4 1.0
10.8 1.1
14.2 1.4

In nitric acid medium under Ar, W0(H2O2) is increased by about


2.3 times compared to pure water. This observation is in agreement
with the literature and results from the reaction of OH radicals with
nitrate ions and the subsequent hydrolysis of the generated nitrate
radical as discussed above (reactions (13) and (14)) [16,17,21]. The
sonication of an equivalent nitric solution under Ar/O2 atmosphere
allows further increase in H2O2 accumulation rate compared to that
under Ar (3.5 times higher than what observed in pure water; 1.6
times higher in comparison to nitric medium). Note however that
the relative increase of W0(H2O2) under Ar/O2 atmosphere is less
important in nitric medium than in pure H2O (nitric medium:
W 0 H2 O2 Ar=O2 /W0(H2O2)Ar = 1.6; pure water: W 0 H2 O2 Ar=O2 /
W0(H2O2)Ar = 2.5). Finally, one can conclude that at 20 kHz the
combination of Ar/O2 atmosphere and nitric acid medium (with
anti-nitrous reagent) allows observing the highest accumulation
rate of H2O2.

3. Results and discussion


3.1. H2O2 accumulation rate
3.1.1. Low frequency
The kinetics of H2O2 formation during 20 kHz sonolysis of pure
water and 1 M HNO3 in presence of 0.1 M [N2H5NO3] solution
under Ar and Ar/(20 vol.%)O2 atmospheres are shown in the
Fig. 1. Hydrogen peroxide is formed according to zero-order kinetics with initial rates (W0(H2O2)) presented in the Table 1. In agreement with the literature, the formation rates observed in pure
water are more than doubled under Ar/O2 when compared to formation rates solely under Ar [7]. This phenomenon is explained by
the scavenging of H radicals with molecular O2 inside the cavitation bubbles (reaction (18)). This reaction avoids the recombination reaction between H and OH radicals and generates
hydroperoxyl radicals leading to H2O2 formation in agreement
with the reaction (19).

H O2 ! HO2

18

2HO2 ! H2 O2 O2

19

3.1.2. High frequency


The Fig. 2 illustrates the formation kinetics of H2O2 in pure water
and 1 M HNO3 (in the presence of 0.1 M [N2H5NO3]) under Ar or
Ar/O2 for high frequency ultrasound (207 and 615 kHz). Similar to
20 kHz, hydrogen peroxide is formed with zero-order kinetics.
Whatever the experimental conditions, the H2O2 yields (G, lmol J1)
given in Table 2 are found to be increased for high frequency
experiments, in agreement with the literature [12]. These results
have been explained by several phenomena occurring under high
frequency ultrasound: (i) the increased number of cavitation bubbles [23], (ii) the shortened ultrasound wave periods and increased
bubble surface-to-volume ratio (S/V) leading to enhanced rectified
diffusion [2,24], and (iii) the higher intrabubble vibronic temperatures providing higher dissociation degree of O2 [12,25].
Under Ar, G values are found to be higher in aqueous nitric
solution when compared to pure water in agreement with the
experiments and mechanisms described at 20 kHz (Fig. 1).
However, under Ar/O2 atmosphere, surprisingly, an inversed

Fig. 1. Hydrogen peroxide accumulation as a function of sonication time (20 kHz, 0.37 W mL1) in pure water (blue curve) and 1 M HNO3/0.1 M [N2H5NO3] (red curve) under
Ar (a) or Ar/O2 (b) atmosphere (T = 21 C). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

E. Dalodire et al. / Ultrasonics Sonochemistry 29 (2016) 198204

201

Fig. 2. Kinetics of hydrogen peroxide accumulation as a function of sonication time (615 kHz at 0.17 W mL1 and 207 kHz at 0.16 W mL1) in pure water (blue curve) and 1 M
HNO3/0.1 M [N2H5NO3] (red curve) under Ar (a) and Ar/O2 (b) gas (T = 21 C). (For interpretation of the references to color in this figure legend, the reader is referred to the
web version of this article.)

Table 2
Hydrogen peroxide energetic yields (G, lmol kJ1) measured during sonolysis of H2O
and 1 M HNO3 (in presence of 0.1 M NH) in the presence of Ar and Ar/O2 as a function
of ultrasonic frequency (T = 21 C).
G in lmol kJ1
f (kHz)

20
207
615
615

H2O

1 M HNO3/0.1 M NH

Ar

Ar/O2

Ar

Ar/O2

0.05
0.22
0.25
0.30

0.13
1.52
1.40
1.56

0.11
0.45
0.46
0.48

0.18
1.10
1.06
1.13

tendency is observed: higher yields of H2O2 are measured in pure


water in comparison to nitric media (Fig. 2). This inversed tendency is also confirmed when increasing the applied acoustic
power to 0.21 W mL1 (Fig. 3). This can be attributed to an increase
of the number of active cavitation bubbles and the size (Rmax) of
individual bubbles (higher potential energy) [26]. The higher yields
of H2O2 observed at higher ultrasonic frequencies in pure water are
attributed to a more effective O2 dissociation inside the cavitation
bubble (reactions (20)(22)) [9,12].

O2 ! ! 2 O

20

O OH ! HO2

21

O H2 O ! OH OH

22

In order to explain the unexpectedly low yields observed for


H2O2 at high-frequency ultrasound in nitric acid solutions under
Ar/O2 gas mixture, further studies have been performed: (i) effect
of anti-nitrous reagent, (ii) formation of NOx gases, and (iii) formation of HNO2 in the absence of anti-nitrous reagents.
3.2. Effect of anti-nitrous reagent
To evaluate the role of the anti-nitrous reagent, the kinetics of
H2O2 formation was studied in nitric media in the presence of sulfamic acid (NH2SO3H) as an alternative to NH. This reagent, having
a low reactivity towards OH, has been already successfully used in
nitric medium as HNO2 scavenger [21]. H2O2 formation kinetic
curves obtained in 1 M HNO3 in the presence of 0.1 M NH2SO3H or
of 0.1 M [N2H5NO3] under Ar or Ar/O2 at 615 kHz (T = 21 C,
0.17 W mL1) are compared in the Fig. 4. Hydrogen peroxide is
formed with zero-order kinetics and the corresponding formation
rates and energetic yields are presented in the Table 3. No significant
differences are observed between the two anti-nitrous reagents
whatever the gaseous atmosphere. In conclusion, the anti-nitrous
reagent has no displayed effect on H2O2 kinetic formation.
3.3. NOx formation
Another hypothesis to explain the inverse tendency observed
under Ar/O2 atmosphere is linked to nitric medium sonolysis at

Fig. 3. Hydrogen peroxide accumulation as a function of sonication time (615 kHz at 0.21 W mL1) in pure water (blue curve) and 1 M HNO3/0.1 M [N2H5NO3] (red curve)
under Ar (a) and Ar/O2 (b) gas (T = 21 C). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

202

E. Dalodire et al. / Ultrasonics Sonochemistry 29 (2016) 198204

Fig. 4. Hydrogen peroxide accumulation as a function of time in 1 M nitric acid in


the presence of 0.1 M sulfamic acid (red curve) or 0.1 M hydrazinium nitrate (blue
curve) under Ar or Ar/O2 atmosphere at high frequency (615 kHz at 0.17 W mL1),
T = 21 C. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)

high frequency ultrasound. Nitrogen oxides formed during sonolysis of nitric acid [17] are not scavenged by anti-nitrous reagents
and could react with H2O2 leading to the drop in its overall reaction
yield. This possibility is evaluated by measuring the formation of
NOx (NO + NO2) in the gas phase by mass spectrometry. Under
our conditions, NOx species are assumed to result from HNO2
degradation under ultrasound (reaction (5)). The Fig. 5 illustrates
NO formation kinetics observed in 3 M HNO3 at 21 C under Ar
or Ar/O2 at low frequency (20 kHz at 0.37 W mL1) and high frequency (615 kHz at 0.17 W mL1). Note that these experiments
were carried out in 3 M HNO3 to facilitate the observation of the
sonochemical effects. The emission of NO2 was however not
detected in our experiments for all studied ranges of the studied
conditions. Under Ar, NO was observed after 60 min of sonolysis
and the production rate increases significantly with the applied
ultrasonic frequency. This phenomenon is in agreement with the
higher sonochemical yields generally reported for high frequency
ultrasound [17]. These results further demonstrate that the yields
of nitric acid sonolysis are highly dependent upon the applied
ultrasonic frequency. In relatively diluted nitric solutions, the
decomposition reactions of nitrate ions are assumed to occur at
the bubble/solution interface. Cavitation bubble sizes are known
to be smaller at high frequency than at low frequency ultrasound;
the exchange surface (or S/V ratio) is therefore supposed to
increase with the applied acoustic frequency implying an increased
reactivity of nitrate ions concentrated in the overheated bubble
shell. This phenomenon can also be increased with a higher concentration of bubbles under high-frequency ultrasound [23].
Under Ar/O2 atmosphere, NO is not observed in the gas phase
whatever the applied acoustic frequency (Fig. 5). This observation
can be explained by an oxidation reaction of NO with O2 inside the
cavitation bubble similar to that observed in the Ostwald process
related to HNO3 production (reaction (23)) [27,28]. In these conditions, NO formed as a result of HNO2 sonolysis may be considered
as an O2 consumer inside the cavitation bubbles. As the formation

Fig. 5. NO signal followed by mass spectrometry as a function of sonication time in


3 M nitric acid under Ar or Ar/O2 atmosphere at low and high frequencies (20 kHz,
0.37 W mL1, or 615 kHz, 0.17 W mL1), T = 21 C.

rate of H2O2 under Ar/O2 is known to be highly dependent upon the


concentration of O2 in the gas phase, a decrease of O2 concentration in the bubble core would lower H2O2 formation rate in nitric
solutions. Note however that NO2 was not observed by mass spectrometry. Previous studies showed that NO2 can be observed when
HNO2 steady state is reached under sonication [17]. The absence of
NO2 in the gas phase can also be related to its subsequent hydrolysis or reaction with O2 as described by Vialard (reaction (23) and
(24)) and also evidenced in Ostwald process [27,28]
2

2NO O2 ! 2NO2 k23 2:1  109 cm6 mol

s1 29

3NO2 H2 O ! 2H 2NO3 NO k24 4:7  1013 s1 30


24
4NO2 O2 2H2 O ! 4H 4NO3

25

It can be thus concluded that the observed inhibition of H2O2


formation in nitric acid solutions in the presence of oxygen is most
probably not related to the direct interaction of H2O2 with NOx but
rather to oxygen scavenging. Such a conclusion presumes a more
efficient sonolysis of HNO3 at high-frequency ultrasound leading
to higher yields of NOx species. However, the quantification of
NOx is quite a difficult task. The kinetics of HNO2 sonochemical
formation was therefore studied during HNO3 sonolysis in the
absence of anti-nitrous reagents in order to verify this hypothesis.
3.4. HNO2 formation
The Fig. 6a illustrates the HNO2 formation kinetics measured in
3 M HNO3 at 21 C under Ar or Ar/O2 atmosphere at low (20 kHz at
0.37 W mL1) and high frequencies (615 kHz at 0.17 W mL1). In
fact, the measured HNO2 concentration ([HNO2]obs) is lower than
its overall concentration ([HNO2]tot) due to the rapid secondary
reaction with H2O2 (reaction (10)). The Fig. 6b shows the evolution
of [HNO2]tot with the time of sonolysis calculated using the reactions (10) and (26). In this equation, [H2O2] values were obtained

Table 3
Hydrogen peroxide formation rates (W0(H2O2), lM min1) and energetic yields (G, lmol kJ1) observed in 1 M nitric medium in the presence of 0.1 M sulfamic
acid or 0.1 M hydrazinium nitrate under Ar or Ar/O2 atmosphere at high frequency ultrasound (615 kHz at 0.17 W mL1), T = 21 C.
1 M HNO3/0.1 M NH

W0(H2O2) in lM min
G in lmol kJ1

1

23

1 M HNO3/0.1 M NH2SO3H

Ar

Ar/O2

Ar

Ar/O2

4.7 0.5
0.46

10.8 1.1
1.06

4.6 0.5
0.45

11.6 1.2
1.1

E. Dalodire et al. / Ultrasonics Sonochemistry 29 (2016) 198204

203

Fig. 6. HNO2 formation rate as a function of sonication time in 3 M nitric acid under Ar and Ar/O2 atmosphere at low frequency (20 kHz at 0.37 W mL1) (blue curve) and high
frequency ultrasound (615 kHz at 0.17 W mL1) (red curve), after reaction with H2O2 (a) and before reaction with H2O2 (b), T = 21 C. Note that low frequency values are
corrected with results obtained in 1 M HNO3 media. Previous investigations showed that HNO3 is no more affecting H2O2 formation rate when its concentration is above 1 M
[20]. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Table 4
HNO2 formation rate (W0(HNO2)) and energetic yields (G) measured in 3 M nitric acid
under Ar and Ar/O2 atmosphere at low frequency (20 kHz at 0.37 W mL1) and high
frequency ultrasound (615 kHz at 0.17 W mL1), after reaction with H2O2 (obs) and
before reaction with H2O2 (tot), T = 21 C.
615 kHz

20 kHz

Ar

Ar/O2

Ar

Ar/O2

W0(HNO2)obs in lM min
W0(HNO2)tot in lM min1

6.9 0.7
16.6 1.2

2.9 0.3
16.8 1.7

7.5 0.8
9.3 0.9

5.3 0.5
9.3 0.9

Gobs in lmol kJ1


Gtot in lmol kJ1

0.7
1.6

0.3
1.7

0.3
0.4

0.2
0.4

1

Acknowledgments

from the kinetic data reported in the presence of anti-nitrous


reagents. The corresponding formation rates and energetic yields
are presented in the Table 4.

HNO2 tot HNO2 obs H2 O2 

proposed therefore decreasing the amount of O2 available in the


saturated atmosphere which decreases H2O2 formation rate in
nitric media. NO2 thereby generated may act as a NO producer or
O2 consumer. More generally, this study also demonstrates that
opposite effects can be driven under ultrasound when changing
the applied acoustic frequency. Careful investigations of the
involved parameters have to be taken into account when
transposing experiments to different frequencies.

26

In agreement with NO measurements (Fig. 5), the Fig. 6b confirms that HNO3 sonolysis is more efficient at higher ultrasonic
frequency even at lower specific acoustic power compared to
20 kHz. On the other hand, Fig. 6b reveals that the kinetics of
HNO2 formation is not influenced by oxygen for studied
Ar/(20 vol.%)O2 gaseous mixture. This striking feature can be
understood by taking into account that at our studied conditions,
HNO2 is produced mostly by the degradation of nitrate-ion in the
liquid reaction zone surrounding the cavitation bubbles. As a
consequence of the latter process, the concentration of O2 inside
the bubble at collapse is considerably reduced therefore decreasing
its available amount for H2O2 production.
4. Conclusion
In this study, the formation rate of H2O2 in sonicated aqueous
nitric solutions is investigated under various experimental
conditions. At 20 kHz, the formation rate of hydrogen peroxide
formation is found to be enhanced in nitric media whatever the
bubbling gas (but is nevertheless higher under Ar/O2 atmosphere)
when compared to pure water. This observation is confirmed for
high frequency ultrasound under Ar. An opposite effect is however
observed at high frequency under Ar/O2 where a higher formation
rate of H2O2 is observed in pure water. Under Ar/O2, a more important decomposition of nitric acid is evidenced at high frequency
and the absence of NO is reported in the gas phase under Ar/O2.
An oxidation reaction of NO with O2 inside the acoustic bubble is

The authors acknowledge CEA/DEN financial support (PAREC)


and thank Laurent Venault for helpful discussion.
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