Ultrasonics Sonochemistry 73 (2021) 105511

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Ultrasonics Sonochemistry
journal homepage: [Link]/locate/ultson

Insight into the impact of excluding mass transport, heat exchange and
chemical reactions heat on the sonochemical bubble yield: Bubble
size-dependency
Aissa Dehane a, Slimane Merouani b, *, Oualid Hamdaoui c, Abdulaziz Alghyamah c
a
Laboratory of Environmental Engineering, Department of Process Engineering, Faculty of Engineering, Badji Mokhtar – Annaba University, P.O. Box 12, 23000 Annaba,
Algeria
b
Laboratory of Environmental Process Engineering, Department of Chemical Engineering, Faculty of Process Engineering, University Salah Boubnider-Constantine 3, P.O.
Box 72, 25000 Constantine, Algeria
c
Chemical Engineering Department, College of Engineering, King Saud University, P.O. Box 800, 11421 Riyadh, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: Numerical simulations have been performed on a range of ambient bubble radii, in order to reveal the effect of
Sonochemistry mass transport, heat exchange and chemical reactions heat on the chemical bubble yield of single acoustic
Chemical bubble yield bubble. The results of each of these energy mechanisms were compared to the normal model in which all these
Heat transfer
processes (mass transport, thermal conduction, and reactions heat) are taken into account. This theoretical work
Mass transport
was carried out for various frequencies (f: 200, 355, 515 and 1000 kHz) and different acoustic amplitudes (PA:
Chemical reactions
Numerical simulation 1.5, 2 and 3 atm). The effect of thermal conduction was found to be of a great importance within the bubble
internal energy balance, where the higher rates of production (for all acoustic amplitudes and wave frequencies)
are observed for this model (without heat exchange). Similarly, the ignorance of the chemical reactions heat
(model without reactions heat) shows the weight of this process into the bubble internal energy, where the yield
of the main species ( OH, H , O and H2) for this model was accelerated notably compared to the complete model
• •

for the acoustic amplitudes greater than 1.5 atm (for f = 500 kHz). However, the lowest production rates were
registered for the model without mass transport compared to the normal model, for the acoustic amplitudes
greater than 1.5 atm (f = 500 kHz). This is observed even when the temperature inside bubble for this model is
greater than those retrieved for the other models. On the other hand, it has been shown that, at the acoustic
amplitude of 1.5 atm, the maximal production rates of the main species ( OH, H , O and H2) for all the adopted
• •

models appear at the same optimum ambient-bubble size (R0 ~ 3, 2.5 and 2 µm for, respectively, 355, 500 and
1000 kHz). For PA = 2 and 3 atm (f = 500 kHz), the range of the maximal yield of OH radicals is observed at the
•

range of R0 where the production of OH, O and H2 is the lowest, which corresponds to the bubble temperature at
•

around 5500 K. The maximal production rate of H , O and H2 is shifted toward the range of ambient bubble radii
•

corresponding to the bubble temperatures greater than 5500 K. The ambient bubble radius of the maximal
response (maximal production rate) is shifted toward the smaller bubble sizes when the acoustic amplitude
(wave frequency is fixed) or the ultrasound frequency (acoustic power is fixed) is increased. In addition, it is
observed that the increase of wave frequency or the acoustic amplitude decrease cause the range of active
bubbles to be narrowed (scenario observation for the four investigated models).

collapse of the bubbles adiabatically compresses entrapped gas and

1. Introduction vapor, which results in short and local hot spots [3], where the tem­
perature and pressure are around 5000 K and 300 atm, respectively, or
Acoustic cavitation is the formation and collapse of bubbles in liquid more inside the bubbles at the end of the collapse [4]. In this situation,
irradiated by intense ultrasound [1]. Cavitation serves as a means of entrapped molecules of dissolved gases, vaporized water and solutes can
concentrating the diffuse energy of sound. It is the underlying phe­ be brought to an excited state and dissociate [5]. As a result, water vapor
nomenon responsible for sonochemistry and sonoluminescence [2]. Fast and noncondensable gas present inside the hot spots leads to the

* Corresponding author.
E-mail address: [Link]@[Link] (S. Merouani).

[Link]
Received 31 December 2020; Received in revised form 14 February 2021; Accepted 3 March 2021
Available online 11 March 2021
1350-4177/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
([Link]
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

Nomenclature Pv Vapor pressure of water, (Pa).

Pg0 Initial gas pressure, (Pa).
Af (Ar) Pre-exponential factor of the forward (reverse) reaction, R Radius of the bubble, (m).
[(cm3 mol− 1 s− 1) for two body reaction and (cm6 mol− 2 Rmax Maximum radius of the bubble, (m).
s− 1) for three body reaction]. R0 Ambient bubble radius, (m).
bf (br) Temperature exponent of the forward (reverse) reaction. t Time, (s).
c Speed of sound in the liquid medium, (m s− 1). T Temperature inside a bubble, (K).
Eaf (Ear) Activation energy of the forward (reverse) reaction, (cal Tmax Maximum temperature inside a bubble, (K).
mol− 1). T∞ Bulk liquid temperature, (K).
f Frequency of ultrasonic wave, (Hz). xi Solubility (in mole fraction) of the gas i in water.
Ia Acoustic intensity of ultrasonic irradiation, (W m− 2). yH2O Mole fraction of water vapor trapped at the collapse.
kf (kr) Forward (reverse) reaction constant, [(cm3 mol− 1 s− 1) for
two body reaction and (cm6 mol− 2 s− 1) for three body Greek letters
reaction]. γ Specific heat ratio (cp/cv) of the gas mixture.
p Pressure inside a bubble, (Pa). σ Surface tension of liquid water, (N m− 1).
pmax Maximum pressure inside a bubble (Pa). ρ Density of liquid water, (kg m− 3).
p∞ Ambient static pressure, (Pa). λ Gas thermal conductivity (W m− 2 K).
PA Amplitude of the acoustic pressure, (Pa).

formation of a variety of radicals and highly reactive species such as Unfortunately, this is not the case in practice, where a range of ambient
hydroxyl ( OH), hydrogen (H ), hydroperoxyl (HO2) and hydrogen bubble radii is produced depending on the power and frequency of the
• • •

peroxide (H2O2) [6]. The generated substances are able to initiate other acoustical wave and the other experimental conditions [17,40–44].
secondary chemical reactions [7,8]. In general, three distinct regions are Consequently, each bubble will be affected differently depending on its
probable for chemical reactions to occur: within the hot bubble cavity size.
(gaseous region), at the interface between the bubble and bulk liquid, To the best of our knowledge, the effect of mass transport, heat ex­
and in the bulk media [9]. Ultrasonic irradiation (sonolysis) is one of the change and chemical reactions heat on bubble kinetics investigated on a
efficient methods of advanced oxidation processes (AOP) [10]. range of ambient bubble radii is until now not examined previously. The
Now, many researches (theoretical and experimental) are focused to present theoretical study states, for the first time, the effective depen­
study and increase the rates of sonochemical reactions in order to use dence of the ignorance of transfer phenomenons and reaction heats to
them in industry [11]. Hua et al. [12] investigated the effect of ultra­ the initial ambient bubble size. This issue has been treated for an
sound frequency (from 205 to 1071 kHz), nature and ratios of saturating acoustic amplitude ranging from 1.5 to 3 atm and ultrasonic frequency
gases (Ar and O2) on sonoluminescence and sonochemistry, in addition, of 200, 355, 515 and 1000 kHz. The numerical simulations performed in
the impact of hydroxyl radical scavenger and bicarbonate ion was also this work are based on a model of a single bubble (argon bubble).
examined. An optimal frequency of 358 kHz was determined for the
maximal sonoluminescence and chemical reaction rates. In addition, the 2. Model
importance of O2 in sonoluminescence quenching was demonstrated,
and a ratio of 75%Ar/25%O2 was found to be ideal for maximal reaction The employed model is based on a set of ordinary differential
rate. Pétrier et al. [13], examined the rate of phenol and carbon tetra­ equations, where the effects of non-equilibrium evaporation and
chloride degradation over a range of ultrasonic frequencies from 20 to condensation of water vapor at the bubble wall, thermal conduction
800 kHz, where an optimal frequency of 200 kHz was determined for the both inside and outside a bubble and chemical reactions are included.
maximal degradation of phenol, conversely, the decomposition of car­ All numerical simulations have been conducted for a bubble oscillating
bon tetrachloride increases proportionally with the frequency increase. in an argon-saturated water. Based on the above assumptions, temper­
In general, the effects of acoustic amplitude [14–18], frequency ature, pressure, bubble radius evolution and bubble wall velocity can be
[18–22], saturating gas [18,23–27], solution temperature [28,29], static determined at any instant. The radial dynamics of the bubble is
pressure [30,31] and other parameters have been widely investigated described by the modified Keller-Miksis equation (Eq. 1), developed by
[32]. Yasui [37]:
On the other hand, some of the theoretical studies focused on the

( ) ( ) ( )[ ( ( )) ]
Ṙ ṁ 3 2 Ṙ 2ṁ 1 Ṙ R
1− + RR̈ + Ṙ 1 − + = 1+ PB (t) − PA sin 2πf t + − P∞ +
C C ρL 2 3C 3CρL ρL C C
( ) ( ) (1)
m̈R Ṙ ṁ ṁ ṁ Ṙṁ R dPB
1− + + Ṙ + + +
ρL C C ρL ρL 2ρL 2CρL CρL dt

effect of each of the energy parameters found in the bubble internal where dots denotes the time derivative (d/dt), R is the radius of the
energy balance, such as mass transport [33,34], chemical reactions heat bubble, C the speed of sound in the liquid, ρL is the density of the liquid,
[35,36], thermal conduction [37], bulk liquid viscosity [38], and pres­ ∙
m is the net rate of evaporation per unit area and unit time and P∞ is the
sure force work [39]]. In general, the impact of these energy parameters ambient static pressure. PA is correlated with the acoustic intensity Ia (or
was investigated for a fixed ambient bubble radius (mean value). power per unit area) as: PA = (2IaρLC)1/2. The liquid pressure PB(t) on

2
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

the external side of the bubble wall is related to the internal pressure P(t) ∑ fi + 2
by the following equation [37]: Cp = k B Ci NA (13)
2
( ) ( )
2σ 4μ ṁ 1 1 Ci, kB, NA and fi are the molar concentration of species i (H2O and Ar)
PB (t) = P(t) − − Ṙ + − ṁ2 − (2)
R R ρL ρL ρg inside the bubble, Boltzmann constant, Avogadro number and the
number of degrees of freedom of species i (fH2O = 6 and fAr = 3),
where σ is the surface tension, µ is the liquid viscosity and ρg is the respectively.
density inside the bubble. The internal pressure P(t) is calculated using The temperature (T) inside bubble is calculated by solving the
Van der Waals equation (Eq. 3): following equation [37]:
nRg T an2 ∫T ∫T
P(t) = + (3) an2
(V − nb) V 2 E = nH2 O Cv,H2 O (T)dT + nAr Cv,Ar (T)dT − (14)
0 0 V
where a and b are the Van de Waals constants, Rg is the universal gas where E is the internal energy of the bubble and CV,H2O(T) (Cv,Ar(T)) is
constant, V is the volume of the bubble [V = 4/3(πR3)], and T is the the isochoric heat capacity of vapor (Argon) at temperature T, given as a
temperature inside the bubble. The Van der Waals constants (a and b) polynomial approximation (expressions are available in Ref. [49]).
are determined by [45]: The change of the internal energy of a bubble (ΔE) in time (Δt), due
⎧ ( ) ( ) to the pressure work, heat of chemical reactions within the bubble,
⎪
⎪ n H2 O nAr
⎪
⎨ a = a H2 O
nt
+ a Ar
nt energy carried by water molecules by evaporation and condensation and
( ) ( ) (4) heat exchange by diffusion at the interface, is expressed by [37,38]:
⎪
⎪ n n
⎪ b = bH O
⎩
H 2 O
+ b Ar
Ar
( )
2
nt nt Δt Tliq − T 4
ΔE = − P(t).ΔV(t) + 4πR2 ṁCv,H2O + 4πR2 Δtλ − πR3 Δt
M H2 O Lth 3
The mass flux of evaporation and condensation at the interface is
expressed using Hertz-Knudsen formula derived from kinetic theory of ∑
25
× ΔHi ri
gases [46]: i=1
[ ] (15)
ρsat
g,H2 O − ρg,H2 O (R)
(5)
where ΔHi and ri are the enthalpy change and the rate of the ith reaction
ṁ = αC(Ts ) .
4
√̅̅̅̅̅̅̅̅̅̅̅̅̅ respectively, the first term in the right-hand side of Eq. 15 is the PV
8Ts Rg work. The second term is the energy carried by evaporating vapor from
C(Ts ) = (6) the surrounding liquid into the bubble and by condensing vapor from
πMH2 O
the bubble into the liquid in Δt. The third term is the energy change due
where α is the evaporation coefficient (considered constant α = 0.4), to the thermal conduction. The last term is the heat of chemical reactions
C(Ts ) is the average velocity of molecules, ρg,H2O(R) is the density of taking place inside the bubble during the collapse.
water vapor in the bubble: ρg,H2O(R) = MH2O⋅nH2O10− 3/[4/3(πR3)], and In this work, a scheme of 25 reversible chemical reactions is
ρsat − 3 considered (Table 1), in which K chemical species is involved. The
g,H2 O = 0.0173 Kg m is the saturated vapor density. The temperature
general form of these reversible reactions is given as follows:
of the external bubble surface is Ts = Tliq.
Heat exchange inside and outside the bubble is estimated to be [47]: ∑
K ∑
K
(16)
′
( ) υki Xk ↔ υ′′ki Xk
Tliq − T k=1 k=1
Q̇ = 4π R2 λmix . (7)
Lth
in which υki is the stoichiometric coefficient of the ith reaction and Xk is
{ √̅̅̅̅̅̅ }
R Rχ the chemical symbol for the kth species. The superscript ‘ indicates for­
Lth = min , (8) ward stoichiometric coefficients, while “ indicates reverse stoichio­
π Ṙ
metric coefficients. The production rate U̇k of the kth species can be
λmix, χ and Lth are the heat conductivity, thermal diffusivity of the gas written as a summation of the rate of the variables for all reactions
mixture and the thickness of the thermal boundary layer, respectively. involving the kth species:
The thermal conductivity (λmix) is estimated by [48]:
( ) ( ) 1 dnk ∑
I
(17)
′
n H2 O nAr U̇ k = (υ′′ − υki )ri (k = 1, …, K)
λmix = λH2 O (T) + λAr (T) (9) V dt i=1 ki
nt nt
where nk is the number of moles of the kth species. The rate ri for the ith
where λH2O(T) and λAr(T) are the thermal conductivity of water vapor
reaction is given as:
and argon at temperature T (in K), respectively. The thermal conduc­
tivity (in W m− 1 K− 1) of H2O and Ar are estimated by [45]: ∏
K ′ ∏
K
(18)
′′
ri = kfi [Xk ]υki − kri [Xk ]υki
− 5
λH2O (T) = 9.967213 × 10 T − 1.1705 × 10 − 2
(10) k=1 k=1

λAr (T) = 3.5887 × 10− 5 T + 6.81277 × 10− 3

(11) where [Xk] is the molar concentration of the kth species and kfi and kri are
the forward and reverse rate constants of the ith reaction, respectively.
At the bubble wall, the thermal diffusivity (χ ) is estimated by [47]: The forward and reverse rate constants for the ith reactions are assumed
λmix to have the following Arrhenius temperature dependence:
χ= (12) ( )
Cp Eafi
kfi = Afi T bfi exp − (19)
3 Rg T
where Cp is the heat capacity concentration (J m− K− 1) for H2O and Ar
mixture [47]: (
Eari
)
kri = Ari T bri exp − (20)
Rg T

3
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

Table 1
Scheme of the possible chemical reactions inside a collapsing argon bubble [36,53]. M is the third Body. Subscript “f” denotes the forward reaction and “r” denotes the
reverse reaction. A is in (cm3 mol− 1 s− 1) for two body reaction [(cm6 mol− 2 s− 1) for a three body reaction], and Ea is in (cal mol− 1) and ΔH in (kcal mol− 1). For some of
the backward reactions, the constants are not listed. Those backward reactions are neglected during calculations.
Reaction Af nf Eaf Ar nr Ear ΔH
23 5 22
1 H2O + M ⇌ H + OH + M 1.912 × 10 − 1.83 1.185 × 10 2.2 × 10 − 2.0 0.0 121.72
• •

2 OH + M ⇌ O + H +M 9.88 × 1017 − 0.74 1.021 × 105 4.714 × 1018 − 1.0 0.0 104.36
• •

3 O + O + M ⇌ O2 + M 6.165 × 1015 − 0.5 0.0 4.515 × 1017 − 0.64 1.189 × 105 − 120.91
4 H +O2 ⇌ O+ OH 1.915 × 1014 0.0 1.644 × 104 5.481 × 1011 0.39 − 2.93 × 102 16.54
• •

5 H +O2 + M ⇌ HO2 +M 1.475 × 1012 0.6 0.0 3.09 × 1012 0.53 4.887 × 104 − 49,0
• •

6 O + H2O ⇌ OH+ OH 2.97 × 106 2.02 1.34 × 104 1.465 × 105 2.11 − 2.904 × 103 17.37
• •

7 HO2+H ⇌ H2 + O2 1.66 × 1013 0.0 8.23 × 102 3.164 × 1012 0.35 5.551 × 104 − 57.34
• •

8 HO2+H ⇌ OH+ OH 7.079 × 1013 0.0 2.95 × 102 2.027 × 1010 0.72 3.684 × 104 − 38.82
• • • •

9 HO2+O ⇌ OH + O2 3.25 × 1013 0.0 0.0 3.252 × 1012 0.33 5.328 × 104 − 55.47
• •

10 HO2+ OH ⇌ H2O + O2 2.89 × 1013 0.0 − 4.97 × 102 5.861 × 1013 0.24 6.908 × 104 − 72.83
• •

11 H2 + M ⇌ H +H +M 4.577 × 1019 − 1.4 1.044 × 105 1.146 × 1020 − 1.68 8.2 × 102 106.33
• •

12 O + H2 ⇌ H + OH 3.82 × 1012 0.0 7.948 × 103 2.667 × 104 2.65 4.88 × 103 1.97
• •

13 OH + H2 ⇌ H +H2O 2.16 × 108 1.52 3.45 × 103 2.298 × 109 1.40 1.832 × 104 − 15.4
• •

14 H2O2 + O2 ⇌ HO2+HO2 4.634 × 1016 − 0.35 5.067 × 104 4.2 × 1014 0.0 1.198 × 104 41.95
• •

15 H2O2 + M ⇌ OH+ OH + M 2.951 × 1014 0.0 4.843 × 104 1.0 × 1014 − 0.37 0.0 52.13
• •

16 H2O2 + H ⇌ H2O+ OH 2.410 × 1013 0.0 3.97 × 103 1.269 × 108 1.31 7.141 × 104 − 69.6
• •

17 H2O2 + H ⇌ H2 + HO2 6.025 × 1013 0.0 7.95 × 103 1.041 × 1011 0.70 2.395 × 104 − 15.38
• •

18 H2O2 + O ⇌ OH + HO2 9.550 × 106 2.0 3.97 × 103 8.66 × 103 2.68 1.856 × 104 − 13.42
• •

19 H2O2+ OH ⇌ H2O + HO2 1.0 × 1012 0.0 0.0 1.838 × 1010 0.59 3.089 × 104 − 30.78
• •

20 O3 + M ⇌ O2 + O + M 2.48 × 1020 0 2.27 × 104 – – – 26.14

21 O3 + O ⇌ O2 + O2 5.2 × 1018 0 4.157 × 103 – – – − 94.77
22 O3+ OH ⇌ O2 + HO2 7.8 × 1017 0 1.9 × 103 − 39.46
• •
– – –
23 O3 + HO2 ⇌ O2 + O2+ OH 1 × 1017 0 2.8 × 103 − 29.17
• •
– – –
24 H + O3 ⇌ HO2+O 9 × 1018 0.5 3.99 × 103 32.45
• •
– – –
25 H + O3 ⇌ OH + O2 1.6 × 1019 0 0 − 23.01
• •
– – –

where Rg is the universal gas constant, Afi (Ari) is the pre-exponential bubble composition is a mixture of water vapor and argon. The complete
factor, bfi (bri) is the temperature exponent and Efi (Eri) is the activa­ bubble-dynamics model includes the liquid compressibility and viscos­
tion energy. Arrhenius parameters of each chemical reaction are pre­ ity, heat transfer (i.e., thermal conduction through bubble wall), mass
sented in Table 1. transfer (i.e., nonequilibrium and condensation evaporation of the
The water vapor change with time inside the bubble, due to the liquid vapor across the bubble/liquid interface), and reaction kinetics
evaporation and condensation at the bubble wall and due to chemical occurring inside the bubble (i.e., reactions heats are incorporated). In
reactions is given by: order to appreciate the impacts of different parameters injected into the
energy equation, the results of excluding of each of these parameters on
nH2 O (t + Δt) = nH2 O (t) + 4πR2 Δt
ṁ
+ VΔtU̇ H2 O (21) both the dynamics of the single bubble and chemical species generated
MH2O inside the bubble were investigated:
For other species k (except Ar):
∙
1. Q = 0Complete model with including all parameters (i.e., denoted as
nk (t + Δt) = nk (t) + VΔtU̇ k (22)
normal),
The modified Keller-Miksis equation (Eq. 1), is a nonlinear second- ∙
2. m = 0Model without heat transfer (i.e., denoted as Q̇ = 0),
order differential equation, which can be reduced to a system of two 3. Model without mass transfer (i.e., denoted as ṁ = 0),
differential first-order equations as 4. Model without reaction heats (i.e., denoted as ΔH = 0).
dR
= Ṙ (23) Finally, it is important be noted that our study gives a good modi­
dt
fication of Yasui’s model, where some modifications are done. These
⎧ ( )[ ( ) ⎫
⎪
( ( )) ]
m̈R Ṙ ṁ ⎪ changes are given as follows:
⎪ 1 1+ Ṙ PB (t)− PA sin 2πf t+ R
⎪
⎪ − P ∞ + 1− + +⎪
⎪
⎪ A more simplified equation of Hertz-Knudsen formula is used (Eq. 5),
⎪
⎨ρL C C ρL C CρL ⎪
⎬
( ) ( ) compared to that used by Yasui [37]. In addition, in our work, we
⎪
⎪
⎪
⎪ ṁ ṁ Ṙṁ R dPB 3 2 Ṙ 2ṁ
⎪
⎪
⎪
⎪ consider the temperature on the external bubble wall as constant,
⎪
⎩ Ṙ+ + + − Ṙ 1− + ⎪
⎭ conversely to Yasui’s studies.
dṘ ρL 2ρL 2CρL CρL dt 2 3C 3CρL
= ( ) For the heat exchange mechanism, a good combination is introduced
dt
1− CṘ +Cṁρ R by the adoption of Toegel’s heat model (for heat conduction, Eq. 7) [50],
which is not the case for the Yasui’s model.
L

(24)
3. Results and discussion
Eqs. (14), (23) and (24) are solved using finite difference method.
The outputs of these equations are the bubble wall velocity, evolution of
In this section, the effect of the different models on the production
the bubble radius, variation of bubble temperature and pressure all
rates of the main species is discussed. As it is known, the main species
along the bubble oscillation, respectively. The variation in time of
created inside an argon bubble are O, H , OH and H2 [26,51–54]. Based
• •

number of moles of each species housed within the bubble is given by

on this observation we limit our work to these principal species. The
Eqs. (21) and (22). The amount of argon remains unchanged during the
simulations were performed at frequencies of 200, 355, 500 and 1000
bubble oscillation (i.e., chemically inert).
kHz. The selection of this range of ultrasound frequency (200, 355, 500
In the present study, all simulations were conducted for a single
and 1000 kHz) is based on many experimental works, which found that
bubble oscillating in an argon-saturated water at 20 ◦ C, so, the initial

4
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

(a) PA = 1.5 atm (f = 200 kHz): OH, H

H=0)
H=0)

Production rate of OH (mol/s) 2E-11 1,6E-11

Production rate of H (mol/s)

1,8E-11 1,4E-11
Production rate of OH (mol/s)

1,6E-11

Production rate of H (mol/s)

1,2E-11
1,4E-11
1,2E-11 1E-11

1E-11 8E-12
8E-12 6E-12
6E-12
4E-12
4E-12
2E-12 2E-12

0 0
16 14 12 10 8 6 5 3,6 3,2 2,4 2 1,7 1,5 1,4 1,3 1,2 1,1 1
R0 (µm)
µm)

(b) PA = 1.5 atm (f = 200 kHz): O, H2

O (Normal) O (Q=0) O (m=0) O ( H=0)

H2 (Normal) H2 (Q=0) H2 (m=0) H2 ( H=0)
2E-11 1,8E-11

Production rate of H2 (mol/s)

Production rate of O (mol/s)

1,8E-11 1,6E-11
Production rate of O (mol/s)

1,6E-11

Production rate of H2 (mol/s)

1,4E-11
1,4E-11
1,2E-11
1,2E-11
1E-11
1E-11
8E-12
8E-12
6E-12
6E-12
4E-12 4E-12

2E-12 2E-12

0 0
16 14 12 10 8 6 5 3,6 3,2 2,4 2 1,7 1,5 1,4 1,3 1,2 1,1 1
R0 (µm)
R0 (µm)
Fig. 1. (a)-(h). Production rates of OH, O, H and H2 over a wide range of R0 for the model without thermal conduction (Q̇ = 0), model without mass transport (ṁ =
• •

0), or model without reactions heat (ΔH = 0), compared to the complete model (normal) (PA = 1.5 atm, frequency = 200, 355, 500 and 1000 kHz).

the best frequency for sonochemistry is ranged from 200 to 1000 kHz The liquid ambient temperature is 20 ◦ C. These production rates are
[12–14,18,20,55–59]. These work confirmed that lower frequencies (i. given for models without mass transport, without thermal conduction
e., usually 20 kHz) is not suitable for producing efficient sonochemical and without reactions heat, compared to the compete model (i.e.,
effects. denoted as normal). In Fig. 2(a)-(d), the production rates of these species
( OH, H , O and H2) are shown for the acoustic amplitudes of 2 and 3 atm
• •

3.1. Models effects on production rates under the ultrasound frequency of 500 kHz. The rest of conditions are
the same as in Fig. 1. The production rate in all these figures is defined as
In Fig. 1(a)-(f), the production rates for the essential species ( OH, H ,
• •
the amount of each indicated species created inside the bubble at the end
O and H2) produced inside an argon saturated water bubble are shown of the bubble collapse multiplied by the driving frequency [54,60,61]. In
for the ultrasound frequencies of f = 200, 355, 500 and 1000 kHz over a Fig. 3(a)-(f), temperature profiles are given for the acoustic amplitude of
wide range of ambient bubble radius (R0), where the acoustic amplitude 1.5 atm (f = 200, 355, 500 and 1000 kHz) and for PA = 2 and 3 atm
and the ambient pressure are maintained at 1.5 and 1 atm, respectively. under the ultrasound frequency of 500 kHz. Temperatures of these

5
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

Fig. 1. (continued).

profiles are the maximum values achieved at the end of the first bubble importance of heat transfer into bubble internal energy balance espe­
collapse (at the maximum compression of the bubble) during the bubble cially during the compression phase [37]. Bubble internal energy in­
oscillation. creases during the compression phase due to the work applied on bubble
As it is expected, the production rate of the different species (for all wall by the external liquid. However, some energy should be carried out
the adopted models) is increased by the decrease of the ultrasound by thermal conduction and vapor condensation. Therefore, the un­
frequency, Fig. 1(a)-(h), or if the acoustic power is increased Fig. 2(a)- awareness of heat transfer mechanism increases largely bubble tem­
(d). These finding are similar to those found by Sochard et al.[62], Yasui perature, thus the production rates of different species created inside
et al. [30,60] and Merouani et al. [31,61,63]. This increase of production bubble increases (i.e., the increase of bubble temperature increases the
rate is clearly observed at around a determined ambient bubble size (R0 thermal dissociation of water vapor, consequently, the yield of the other
of the maximal response), where the acoustic parameters (frequency and species is surely increased). This conclusion is reinforced by the absence
amplitude) are suitable to get a maximal intensity of response. The of the oxidant consumer. In addition, this increase of temperature inside
predominance of the thermal conduction mechanism is confirmed the bubble is promoted when the temperature on the external bubble
through the production rates obtained when the model without heat wall is considered constant, as it is done here in our work by using Toegel
conduction is adopted compared the other models (normal model and model [50] for heat transfer. It is also observed in Fig. 1(a)-(h) that the
models without mass transport or reaction heat). This sensitivity to the production rate of the different species ( OH, H , O and H2) using the
• •

heat transfer mechanism is observed for all the acoustic amplitudes and model without mass transfer is greater than that of the model without
frequencies [Figs. 1(a)-(h) and 2(a)-(d)], even when the temperature reactions heat or the normal model, which is explained by the lower
obtained using the model without mass transfer is greater than that of acoustic amplitude (PA = 1.5 atm) used in this case (lower expansion
the model without thermal conduction (Fig. 3(f)). This is because of the and compression ratios). Due to this low acoustic power, we can see

6
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

(e) PA = 1.5 atm (f = 500 kHz): OH, H

3E-16
5E-17

4E-17
Production rate (mol/s)

2,5E-16
3E-17

2E-16 2E-17

1E-17

1,5E-16 0
9 6 4 3 2,5 2 1,5 1

1E-16

5E-17

0
9 6 4 3 2,5 2 1,5 1
o

(f) PA = 1.5 atm (f = 500 kHz) O, H2

O (Normal) O (Q = 0) O (m = 0)
H (Normal) H (Q = 0) H (m = 0) H
2,5E-21 5E-23 7E-18

Production rate of H (mol/s)

4E-23
Production rate of O (mol/s)

3E-23
6E-18
2E-21
2E-23
5E-18
1E-23
1,5E-21
0 4E-18
9 6 4 3 2,5 2 1,5 1
3E-18
1E-21

2E-18
5E-22
1E-18

0 0
9 6 4 3 2,5 2 1,5 1
Ro(µm)

Fig. 1. (continued).

easily in Fig. 3(a)-(d) that the peak temperatures attained for the four frequencies).
frequencies (5100, 3500, 2500 and 1300 K for 200, 355, 500 and 1000 On the other hand, it is also seen in Fig. 1(a)-(d) that the production
kHz, respectively) are insufficient to reveal especially the impact of the rate of OH, H , O and H2 for the model without reaction heat is greater
• •

reactions heat compared to the mass transport mechanism. This in spite than that of the normal model. This is because at these conditions of
of the lower amount of vapor housed into bubble for the model without acoustic amplitude and ultrasound frequencies (1.5 atm and 200/355
mass transport. In other worlds, as we know, the condition to get a vi­ kHz), the elimination of the reactions heat starts to give its contribution
olent collapse is the presence of a sufficient quantity of water vapor into bubble internal energy balance. So that, maximal temperature is
inside the bubble during the collapse. Thus, at 1.5 atm, for the model increased compared to the normal model where the endothermal nature
without mass transport we found approximately the same response of the most chemical reactions taking place inside bubble (Table. 1)
(Tmax) as that of the model without reactions heat or the normal model, during collapse causes a decrease of the bubble temperature and
which means that the amount of vapor inside the bubble for the model consequently the production rate [35,37]. In Fig. 1(c)-(d), the maximal
without mass transport is sufficient in this case (1.5 atm, for all production rates of OH, H , O and H2 for the model without reactions
• •

7
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

(g) PA = 1.5 atm (f = 1000 kHz): OH, H

2,5E-23
6E-26
Production rate (mol/s)

4E-26
2E-23
2E-26

1,5E-23 0
4 3 2,5 2 1,5 1

1E-23

5E-24

0
4 3 2,5 2 1,5 1
R0 (µm)

(h) PA = 1.5 atm (f = 1000 kHz): O, H2

O (Normal) O (Q = 0) O (m = 0)
H (Normal) H (Q = 0) H (m = 0) H
1,5E-34 1,2E-26

Production rate of H (mol/s)

Production rate of O (mol/s)

1,3E-34 1E-26

1,1E-34
8E-27
9E-35
6E-27
7E-35
4E-27
5E-35

3E-35 2E-27

1E-35 1E-35
4 3 2,5 2 1,5 1
Ro (µm)

Fig. 1. (continued).

heat are 4.33 × 10− 14, 3.50 × 10− 14, 5.6 × 10− 17 and 4.26 × 10− 15 mol production rate) is shifted toward lower ambient bubble radius as the
s− 1, respectively. This maximum is retrieved at around R0 = 3 µm. ultrasound frequency is reduced (acoustic amplitude is constant) [Fig. 1
However, for the normal model, the production rates of OH, H , O and (a)-(h)]. At the ultrasound frequencies of 200, 355, 500 and 1000 kHz,
• •

− 14 − 14 − 17
H2 are 2.86 × 10 , 2.36 × 10 , 2.52 × 10 and 2.51 × 10− 15 mol the ambient bubble sizes of the maximal response are around 3.2, 3, 2.5
s− 1, respectively, at the same ambient bubble size, i.e., 3 µm. For the and 2 µm, respectively. This result is due to the effect of the ultrasound
ultrasonic frequencies of 500 and 1000 kHz at the acoustic amplitude of frequency. As the ultrasonic frequency is increased, bubbles are found to
1.5 atm, Fig. 1(c)-(f), it is seen that the response (maximal production be enables to largely expand so that the maximal response is automat­
rate) of the model without reactions heat and the normal model is ically shifted toward small bubble radii [64]. Conversely, when the ul­
similar for all the main species ( OH, H , O and H2). This is obviously trasonic frequency is reduced, bubbles will get more time to expand,
• •

explained by the lower maximal temperatures retrieved for the two therefore expansion and compression ratios are higher in this case, and
models on their ranges of ambient bubble radius [Fig. 3(c)-(d)]. the maximal response is moved toward larger bubble radii. This trend is
It should be noted here that the maximal response (maximal observed in the work of Yasui et al. [60], where the intensity of

8
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

a) PA = 2 atm (f = 500 kHz): OH, H

1,2E-11
Production rate (mol/s)

1E-11

8E-12

6E-12

4E-12

2E-12

0
11 9 7 5 4 3,4 2,8 2,3 2 1,8 1,7 1,5 1 0,8 0,65 0,5
R (µm)

(b) PA = 2 atm (f = 500 kHz): O, H2

O (Normal) O (Q = 0) O (m = 0)
H (Normal) H (Q = 0) H (m = 0) H
1,6E-11

1,4E-11
Production rate (mol/s)

1,2E-11

1E-11

8E-12

6E-12

4E-12

2E-12

0
11 9 7 5 4 3,4 2,8 2,3 2 1,8 1,7 1,5 1 0,8 0,65 0,5
Ro (µm)

Fig. 2. (a)-(d). Production rates of OH, O, H and H2 over a wide range of R0 for the model without thermal conduction (Q̇ = 0), model without mass transport (ṁ =
• •

0), or model without reactions heat (ΔH = 0), compared to the complete model (normal) (PA = 2 and 3 atm, frequency = 500 kHz).

sonoluminescence and sonochemical reactions have been studied on a decreased. The same result is shown previously when the ultrasonic
range of ambient bubble radii for an air bubble in liquid water. frequency is changed by considering the acoustic amplitude as constant
Until now, we have only treated the effect of the different models (1.5 atm). On the other hand, the ambient bubble radius of the maximal
(without mass transport, thermal conduction and reactions heat response (maximal production rate) is shifted toward small values. For
compared to the normal model) on production rates by changing the the acoustic amplitudes of 1.5, 2 and 3 atm, the ambient bubble radii of
ultrasound frequency (200, 355, 500 and 1000 kHz) and considering the the maximal production rates are 2.5 , 1.7 and 1.5 µm, respectively,
acoustic amplitude as constant at 1.5 atm. However, to reveal more the under the ultrasound frequency of 500 kHz. Conversely to the previous
impact of these mechanisms on the different productions rates, we fix case where the acoustic amplitude is fixed, the increase of the acoustic
the ultrasonic frequency at 500 kHz and we change gradually the amplitude (from 2 atm) shows that the production rate of the model
acoustic amplitude (1.5, 2 and 3 atm). It should be noted here that the without reactions heat or the normal model is greater than the case of
choice of this ultrasound frequency is arbitrary, because of the behaviors the model without mass transport for all the main species (i.e., OH, H , O
• •

similarity observed for the four frequencies studied herein. and H2) [Figs. 1(e)-(f) and 2(a)-(d)]. This is even if the temperature of
It is seen from Figs. 1(e)-(f) and 2(a)-(d) that the maximal production the model without mass transport is greater than that of the model
rates attained at different ambient bubble sizes are increased when the without reactions heat or the normal model. This behavior is clearly
acoustic amplitude is increased or if the ultrasound frequency is observed when the peak temperature of collapse corresponding to its

9
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

(c) PA = 3 atm (f = 500 kHz) : OH, H

H=0)
H=0)
5E-11 2,5E-10
Production rate of OH (mol/s)

Production rate of H (mol/s)

4E-11 2E-10

3E-11 1,5E-10

2E-11 1E-10

1E-11 5E-11

0 0
9 8 7 6 5 4 3 2 1,6 1,5 1,4 1 0,5 0,2

Ro (µm)
6E-12

4E-12

2E-12

0
9 8 7 6 5 4 3 2 1,6 1,5 1,4 1 0,5 0,2

(d) PA = 3 atm (f = 500 kHz): O, H2

O (Q = 0) O (m = 0)
H (Normal) H (Q = 0) H (m = 0) H
1,6E-10 1,8E-11
Production rate of O (mol/s)

1,6E-11
Production rate of H (mol/s)
1,4E-10
1,4E-11
1,2E-10
1,2E-11
1E-10
1E-11
8E-11
8E-12
6E-11
6E-12
4E-11
4E-12
2E-11 2E-12

0 0
9 8 7 6 5 4 3 2 1,6 1,5 1,4 1 0,5 0,2
Ro (µm)
Fig. 2. (continued).

ambient bubble radius is greater or around 4500 K [Fig. 3(c), (e), and for the model without mass transport. Therefore, the elimination of the
(f)]. This decrease of production rate is due to the endothermal nature of reactions heat increases more bubble temperature and consequently the
the most chemical reactions taking place inside bubble during collapse production rate. Even for the normal model where all the mechanisms
(Table 1) and especially to the elimination of evaporation mechanism are taken into account, the production rate of OH, H , O and H2 in this
• •

10
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

Fig. 3. (a)-(f): The pick temperature profiles over a wide range of R0 for the model without thermal conduction (Q̇ = 0), model without mass transport (ṁ = 0), or
model without reactions heat (ΔH = 0), compared to the complete model (normal) (PA = 1.5 atm for (a)-(d) [frequency = 200, 355, 500 and 1000 kHz] and PA = 2
and 3 atm [f = 500 kHz] for (e) and (f)).

11
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

(d) PA = 1.5 atm (f = 1000 kHz)

T (Normal) T (Q=0) T (m=0) T ( H=0)

1800
1600
1400
1200

T (K)
1000
800
600
400
200
0
0 1 2 3 4 5

(e) PA= 2 atm, (f = 500 kHz)

T (Normal) T (Q=0) T (m=0) T ( H=0)
8000 7500
7000 7100

6000 6700

5000 6300
T (K )

4000 5900

3000 5500
0,5 1,5 2,5
2000

1000

0
0 2 4 6 8 10 12

(f) PA = 3 atm (f = 500 kHz)

T (Normal) T (Q=0) T (m=0) T ( H=0)

25000

20000

15000
T (K)

10000

5000

0
0 2 4 6 8 10 12
Ro (µm)

Fig. 3. (continued).

model is greater than that obtained by the model without mass trans­ of thermal conduction mechanism is found to be dominant when the
port. This is because of the elimination of evaporation mechanism acoustic amplitude is increased [Fig. 2(a)-(d)], which confirms again the
during the expansion phase, so that during the compression phase the importance of energy carried out of the bubble by heat transfer during
ignorance of the condensation mechanisms for the model without mass the compression phase.
transport is insufficient to largely increase its production rate. The effect It should be noted here that for small bubble radii (smaller than R0 of

12
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

the maximal production rate), some interferences of maximal produc­ rate is expected; therefore, bubble energy balance during this phase is
tion rates and temperatures are exhibited by all the adopted models not largely affected by the elimination of reactions heat, which means a
(normal model, and models without mass transport, thermal conduction similar response (production rate and maximal temperature) for the
or reactions heat) as shown in Figs. 1(a)-(h), 2(a)-(d) and 3(a)-(f). This is model without reactions heat compared to the normal model. On the
due to the impact of ambient bubble radius. Because for this range of other hand, a small increase of heat capacity (due to the small expansion
ambient bubble radii, a small amount of vapor is expected to be housed ratio) for the normal model on this range of ambient bubble radii
into bubble at the end of rarefaction phase due to the small expansion compared to the model without mass transport, so that the two models
ratio. Consequently, the difference of vapor amount between the normal give a similar response, in spite of the elimination of condensation
model and the model without mass transport is not large for this range of mechanism for the model without mass transport. Because of the short
ambient bubble radii. During the compression phase, a lower production time of compression and the lower expansion ratio, the heat conduction

kf1 kr1 kf2 kr2

1,E+08
1,E+08 (a)
(b)
1,E+06
1,E+06

1,E+04 1,E+04

1,E+02 1,E+02

1,E+00 1,E+00
0 5000 10000 15000 20000 0 3000 6000 9000 12000 15000 18000 21000

kf3 kr3 kf6 kr6

1,E+08 1E+09

(c) (d)
1,E+06
1E+08

1,E+04

1E+07
1,E+02

1E+06
1,E+00
0 4000 8000 12000 16000 20000
0 5000 10000 15000 20000

kf11 kr11 kf12 kr12

1,E+07
1,E+10
1,E+06
1,E+08
1,E+05

1,E+04 1,E+06

1,E+03
1,E+04
1,E+02
1,E+02
1,E+01

1,E+00 1,E+00
0 4000 8000 12000 16000 20000 0 3000 6000 9000 12000 15000 18000 21000

Fig. 4. (a)-(f). Evolutions vs. temperature of the forward and reverse rate constant of reactions (1), (2), (3), (6), (11) and (12) of Table 1. Unit: (cm3 mol− 1 − 1
s ) for
two body reaction and (cm6 mol− 2 s− 1) for a three body reaction.

13
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

during the compression phase for the normal model is very lowered, and H2, the maximal production rate is observed at R0 = 1.7 µm, where
which implies that the maximal production rates (and temperatures) the peak temperatures at this ambient bubble radius for the model
obtained by this model is relatively the same as the model without without thermal conduction and the rest of models are 7400 and 6300
thermal conduction. K, respectively [Fig. 3(e)]. On the other hand, for the model without
Similar interferences are also observed at larger ambient bubble radii thermal conduction, the maximal production rate of OH radicals is
•

(greater than R0 of the maximal response) for all the acoustic amplitudes given at around 2.8 µm, where the peak temperature at this ambient
and the ultrasound frequencies. Because, for this range of ambient bubble radius is 5892 K. This maximal production rate is shifted at
bubble radii, lower expansion and compression ratios are expected and around R0 = 2.3 µm for the rest of models (normal model, and models
also a huge amount of vapor is found inside bubble at the end of rare­ without mass transport or reactions heat), where the maximal temper­
faction phase. The result is a milder collapse for all the treated models, ature attained at this ambient bubble size is 5500 K. All these results
which implies that the effect of each of these mechanisms is hidden in originate from the effect of bubble temperature, because at bubble
this range of ambient bubble radius. temperatures at around 5500 K (all models), the thermal dissociations of
According to Figs. 1(a)-(h) and 2(a)-(d), we can see that at lower water vapor is slightly promoted compared to the OH radicals con­
•

acoustic amplitude (PA = 1.5 atm), the maximal production rates of all sumption [Fig. 4 (a) and (b)]. Therefore, the amount of OH, H and O
• •

the main species created inside bubble ( OH, H , O and H2) at collapse radicals increases at this level. It is important to not here that the
• •

appear at the same ambient bubble radius. This is confirmed for all the complete explanation of the yield of all species on a range of bubble
ultrasonic frequencies. Under the ultrasound frequencies of 200, 355, temperature during the collapse period is a long and difficult task.
500 and 1000 kHz (PA = 1.5 atm), the maximal production rates of OH, However, it is interesting to try to explain these productions at around
•

H , O and H2 are shown at 3.2, 3, 2.5 and 2 µm, respectively [Fig. 1(a)- the end of collapse. Consequently, in our study, we focus on the end of
•

(h)]. However, at the acoustic amplitude of 2 atm (f = 500 kHz), the the compression phase (maximum temperature), which is the most
maximal production rate of OH radicals for the normal model and important moment for the maximal production or consumption of
•

models without mass transport or reactions heat is given at around R0 = chemical substances.
2,3 µm (Fig. 2(a)). Some exception is observed for the maximal pro­ On the other hand, the production rate of O radicals is reduced ac­
duction rate of OH radicals for the model without thermal conduction, cording to 6th reaction (Table. 1), especially due to the impact of mass
•

where R0 (of the maximal response) is shifted toward 2.8 µm [Fig. 2(a) action applied by water molecules. The effect of the backward reaction
and (b)]. For the rest of species (H , O and H2), at this acoustic amplitude of 3rd reaction is reduced, because of the relatively larger amount of O
•

(2 atm), the maximal production rates are observed at the ambient radicals compared to O2 molecules. The consumption of H2 molecules is
bubble radius of 1.7 µm. At the acoustic amplitude of 3 atm (f = 500 reduced according to the 11th reaction, due to the effect of H radicals. In
•

kHz), the maximal production rate of OH radicals (for all models) is addition, the production rate of H2 and O radicals (consumption of OH
• •

th
given at R0 = 5 µm, however, the maximal production rates of H , O and and H radicals) is supposed to be improved according to 12 reaction,
• •

H2 are observed at R0 = 1.5 atm (Fig. 2(c)-(d)). The interpretation of all because of its higher backward kinetic constant compared to the forward
these results can be made using the temperatures profiles of the treated one [Fig. 4(f)]. Nevertheless, at the peak temperatures of the model
models and the kinetic constants of some chemical reactions which have without thermal conduction (Tmax ~ 7400 K) or the rest of models (Tmax
an important effect on the production rates of the main investigated ~ 6300 K) [Fig. 3(e)], the decomposition of water vapor and OH radi­
•

species. To address this, in Fig. 4, the kinetic constants of reactions 1, 2, cals is highly promoted [Fig. 4(a) and (b)]. In addition, the consumption
3, 6, 11 and 12 of Table 1 are represented on a temperature range from of O radicals is reduced either by the increase of the backward kinetic
0 to 21000 K. The choice of these chemical reactions is based on their constant of the 3rd reaction or by the decrease of mass action of water
effects on the amount of the main species created into bubble at collapse. vapor into the 6th chemical reaction [Fig. 4(c) and 4(d)].
From Fig. 3(a)-(d), it is seen that the maximal temperatures retrieved The production rate of H2 and O radicals is also increased by the 12th
for all models (expecting that without heat conduction) under the ul­ reaction, where H and OH radicals are consumed. The consumption of
• •

trasound frequencies of 200, 355, 500 and 1000 kHz for PA = 1.5 atm are H2 molecules is reduced [Fig. 4(e)], in spite of the increase of the for­
around 5100, 3500, 2500 and 1400 K, respectively. In Fig. 4(a), it is ward reaction kinetic constant, due to the higher dissociation of OH
•

nd
found that the thermal decomposition of water (for all models) is pro­ radicals according to 2 reaction which liberates a huge amount of O
portionally reduced as the ultrasound frequency is increased. Conse­ and H radicals. By combining all these observations, we can conclude
•

quently, the formation of H , OH and O is reduced [Fig. 4(a) and (b)] as that at bubble temperatures of ~5500 K (PA = 2 atm, f = 500 kHz), the
• •

the ultrasonic frequency is decreased. The production rate of O radicals formation of OH radicals is found to be promoted than that of O, H and
• •

is found to be lowered according to the 3rd reaction of Table 1 and H2 molecules. However, at higher temperatures (greater than 5500 K),
especially the 6th reaction [Fig. 4(c) and 4(d)]. The amount of H2 is the reverse scenario is observed [Fig. 2(a)-(b)].
increased according to 11th reaction [Fig. 4(e)], especially by the mass At PA = 3 atm [Fig. 2(c) and (d)], it is seen that the same trend found
action of H radicals and the lower value of the forward reaction kinetic in the previous case (PA = 2 atm) is observed herein. The maximum
•

constant. According to the 12th reaction, the formation of O and H2 is production rate of OH radicals is given at R0 = 5 µm, where the peak
•

promoted, due to the relatively higher kinetic constant of the backward temperatures attained at this bubble size are around 5500 K (for all
reaction [Fig. 4(f)]. As a result, for all the adopted models under the models). Therefore, the same interpretations made for the previous case
ultrasound frequencies of 200, 355, 500 and 1000 kHz, the formation of of PA = 2 atm are applicable here. On the other hand, the maximal
OH radicals is found to be predominant compared to the other species at temperatures retrieved for the models without thermal conduction,
•

this acoustic amplitude of 1.5 atm. On the other hand, the production without reactions heat, without mass transport or normal model are
rate of H radicals is greater than that of O and H2, where the formation 13768 K (R0 = 1.5 µm), 11577 K (R0 = 1.5 µm), 19946 K (R0 = 0.5 µm)
•

of H2 for these ultrasonic frequencies is favored than that of O radicals. It and 8800 K (R0 = 1.5 µm), respectively [Fig. 3(f)]. It should be noted
should be noted that according to the previous interpretations, the that the peak temperature retrieved for the model without mass trans­
maximal production rates of the main species ( OH, H , O and H2) are port originate from the magnitude of acoustic power applied on bubble
• •

observed at the same ambient bubble radius for each of the ultrasound wall (PA = 3 atm), which promotes the increase of bubble temperature in
frequencies, conversely to the next case where the production rates are the absence of water vapor. The elimination of vapor participates largely
largely affected by the temperature profiles. in the decrease of the bubble heat capacity. Consequently, during the
At the acoustic amplitude of 2 atm (f = 500 kHz), Fig. 2(a) and 2(b), compression phase, the bubble core temperature increases rapidly due
it seems that the yield of the main species is highly affected by tem­ to this decrease of heat capacity, the decrease of energy carried out by
perature profiles shown for each of the used models [Fig. 3(e)]. For H , O condensation and finally the amount of endothermal reactions taking
•

14
A. Dehane et al. Ultrasonics Sonochemistry 73 (2021) 105511

place into the cavitation during the collapse phase. The same trend is analysis, Writing - original draft, Writing - review & editing. Slimane
found in [50,60,65]. For these maximal temperatures, it is clear that the Merouani: Conceptualization, Project administration, Supervision,
thermal dissociation of water vapor and OH radicals is highly promoted Visualization, Writing - review & editing, Methodology, Formal analysis,
•

(for all models). On the other hand, the production rate of H and O is Writing - review & editing. Oualid Hamdaoui: Conceptualization, Su­
•

largely accelerated [Fig. 2(c) and (d)] as it is explained previously for the pervision, Visualization, Validation, Writing - review & editing. Abdu­
case of acoustic amplitude of 2 atm. For H2 [Fig. 2(d)], some stabiliza­ laziz Alghyamah: Visualization, Writing - review & editing.
tion of the production rate is observed compared to its yield for the
acoustic pressure PA = 2 atm [Fig. 2(b)]. This is due to the rapid increase
Declaration of Competing Interest
of the forward reaction kinetic constant compared to that of the back­
ward reaction. Consequently, H2 molecules are highly consumed at
The authors declare that they have no known competing financial
around the bubble temperature of 8000 K (for all models) [Figs. 3(e) and
interests or personal relationships that could have appeared to influence
2(d)]. In spite of the higher temperature found for the model without
the work reported in this paper.
mass transport, it is seen in Fig. 2(c) and (d) that the minimal production
rates of H , O, OH and H2 are observed only for this model. This is
• •

Acknowledgements
because of the elimination of nonequilibrium evaporation and conden­
sation mechanism, which implies that during the compression phase no
This study was supported by The Ministry of Higher Education and
sufficient water vapor is available to increase bubble production. On the
Scientific Research of Algeria (project No. A16N01UN250320180001)
other hand, it is seen from Fig. 2(c) and (d) that the model without
and the General Directorate of Scientific Research and Technological
thermal conduction persists to be dominant compared to the other
Development (GD-SRTD). The authors extend their appreciation to the
models, where all the main species created by this model are greater
Deputyship for Research & Innovation, “Ministry of Education” in Saudi
than those produced by the rest of models. Also, it is shown from Fig. 2
Arabia for funding this research work through the project No. IFKSURG-
(c) and (d) that the production rates of O, OH, H and H2 for the model
• •

1441-501.
without reactions heat is greater than those of the normal model, which
is explained by the introduction of the reactions heat into bubble in­
ternal energy balance for the normal model. Bearing in mind all these References
considerations, it is clear that at lower temperatures (for all models) the
[1] Pankaj, M. Ashokkumar, Theoretical and Experimental Sonochemistry Involving
formation of OH radicals is favored compared to the other main species
•
Inorganic Systems, Springer, 2011. [Link]
(O, H and H2). However, at the higher temperatures, it is found that the 048138869.
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