Ultrasonics Sonochemistry: Elodie Dalodière, Matthieu Virot, Philippe Moisy, Sergey I. Nikitenko
Ultrasonics Sonochemistry: Elodie Dalodière, Matthieu Virot, Philippe Moisy, Sergey I. Nikitenko
Ultrasonics Sonochemistry: Elodie Dalodière, Matthieu Virot, Philippe Moisy, Sergey I. Nikitenko
Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson
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
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.
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].
2HNO2 ! ! NO NO2 H2 O
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
12
13
NO3 H2 O ! NO2 H2 O2
14
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
200
W 0 H2 O2
60Pac
17
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
H O2 ! HO2
18
2HO2 ! H2 O2 O2
19
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.)
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
O2 ! ! 2 O
20
O OH ! HO2
21
O H2 O ! OH OH
22
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
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
s1 29
25
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
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
0.7
1.6
0.3
1.7
0.3
0.4
0.2
0.4
1
Acknowledgments
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
204