i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 8 7 6 7 e1 8 7 7 9

Available online at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/he

A complete analysis of the effects of transfer

phenomenons and reaction heats on sono-
hydrogen production from reacting bubbles: Impact
of ambient bubble size

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 e 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

highlights

Effects of reactions heat and mass and heat transfer on H2 sono-production are studied.

The three energetic parameters are investigated for a range of ambient bubble radii (R0).

The effect the three energetic mechanisms on H2 sono-generation depend on R0 and frequency.

The ignorance of thermal conduction and reactions heat improve the H2 sono-generation.

Excluding mass transport of water vapor lowers the H2 sono-generation.

article info abstract

Article history: Several experimental and computational works have been focused on the production of
Received 16 January 2021 hydrogen by using ultrasonic irradiation. However, the effects of the different ultrasonic
Received in revised form conditions have been analyzed by considering a single value for the ambient bubble radius
27 February 2021 R0 (mean value), which is not the true case as the size of active bubbles in sonicating
Accepted 8 March 2021 medium is an interval rather than a sole value. In the present paper, the impacts of mass
Available online 12 April 2021 transport, heat exchange and chemical reactions heat on the sono-production of hydrogen
are examined over a range of ambient bubble radii. These effects are shown for various
Keywords: ultrasonic frequencies of 355, 500 and 1000 kHz and under a range of acoustic amplitudes,
Sono-hydrogen from 1.5 to 3 atm. The numerical simulations results demonstrated that the increase of the
Bubble size production rate of hydrogen (around R0 of the maximal production rate) is amortized (for
Water evaporation condensation all models) for the wave frequencies of 355 and 500 kHz at higher amplitude (i.e. 3 atm). On
Heat conduction the other hand, the total production rate (around R0 of the maximal response) is increased
Reactions heat proportionally with the reduction of ultrasonic frequency or if the acoustic amplitude is
Numerical analysis increased. The effect of heat exchange mechanism (on H2 and the total production rate)
was found to be dominant whatever the acoustic amplitude or the wave frequency (on all

* Corresponding author.
** Corresponding author.
E-mail addresses: s.merouani@yahoo.fr, s.merouani03@gmail.com (S. Merouani), ohamdaoui@ksu.edu.sa (O. Hamdaoui).
https://doi.org/10.1016/j.ijhydene.2021.03.069
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
18768 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 8 7 6 7 e1 8 7 7 9

the range of R0). It has been demonstrated that at the acoustic amplitudes >1.5 atm (for
f ¼ 355 and 500 kHz) and >2 atm (for f ¼ 1000 kHz), the impacts of chemical reactions heat
and mass transport are clear compared to the normal model throughout a range of bubble
sizes. The ambient bubble size (R0) of the maximal response (maximal production rate) is
shifted toward lower values when the ultrasound frequency or the acoustic amplitude is
raised. In addition, it is observed that the increase in the wave frequency or the decrease in
acoustic amplitude cause a narrowing in the range of active bubbles.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

improvement potential compared to each isolated technique

Introduction (without ultrasound). An interesting review on hydrogen
generation by sonolysis is recently published by Merouani and
It is estimated that the global distribution of energy use is 80% Hamdaoui in a book chapter [18].
fossil fuels, 14% renewable energy and 6% nuclear power [1]. Water sonication in the presence of dissolved gases gen-
However, due to the major problems confronted in our days, erates acoustic cavitatione the formation, growth and violent
which are the climate change and the fossil fuel depletion [2], collapse of millions of bubbles [25]. Temperature of about
a great number of theoretical and experimental researches is 5000 K and pressure of the order of 500 atm, accompanied with
consecrated to either the creation of new and sustainable chemical reactions and sonoluminescence have been shown
sources of energy or the improvement of the existing ones. to be engendered inside the bubble at the end of the strong
Hydrogen is considered as one of the important energy carrier bubbles collapse [26e28]. Reactive free radicals and species
for the future [3], due to its interesting advantages [e.g. highest (i.e.,COH, H, HOC 2 and H2O2) as well as molecular hydrogen
energy content compared to any known fuel (methane, gas- (H2) arise from the pyrolytic reaction of water vapor and gases
oline, diesel, ethanol and methanol)], where the HHV (higher inside the bubble [29e33]. Experimental measurements
heating value) and LHV (lower heating value) are 141.9 kJ g1 showed that the production rate of H2 is 1.25 fold higher than
and 119.9 kJ g1, respectively [4], different forms of storage that of H2O2 [18].
(e.g. gaseous, liquid, or in together with metal hybrid), abun- On the other hand, the subject of hydrogen production by
dance, a clean fuel with no CO2 emissions and can be used in sonolysis (the sono-hydrogen) was widely treated theoreti-
fuel cells for generation of electricity [5e7]. Therefore, cally in order to increase the process efficiency. Besides,
hydrogen is one of the most effective solutions to reduce different models for a single bubble oscillation were adopted;
greenhouse gases (GHG) emissions and oil dependence [8]. someone's ignore transfer phenomenon (i.e., mass and heat
However, unlike fossil fuels, hydrogen is not readily available transfer) [32,34e36], other ones include them and ignore the
in nature, and must therefore be produced [2]. In nature, we heat generated by the chemical reaction inside the bubble
find hydrogen in a combination with other elements, pri- [37e40], while a very limited models include all these ener-
marily with oxygen in water and with carbon, nitrogen and getic mechanisms in the bubble energy balance [29,41e44].
oxygen in living materials and fossil fuels [9]. Merouani et al. [35], studied the mechanism of H2 sono-
Now, hydrogen is mainly used as a chemical substance generation, where the gaseous production (inside the bub-
(petroleum refining, petrochemical industries for ammonia ble) of hydrogen was evidenced compared to its yield in the
and methanol synthesis) rather than a fuel [10]. In general, liquid phase, where the principal reaction responsible of H2
several processes are available for hydrogen production such yield is COH þ HC / H2þO [35]. In addition, the effects of
as pyrolysis and reforming (steam reforming, partial oxidation different parameters were analyzed such as the acoustic
and autothermal steam reforming) of hydrocarbons and coal amplitude [32], ultrasonic frequency [32], wave form [45],
gasification [3,4,10,11]. About 95% of the hydrogen produced liquid temperature [32], saturation gas [32], alcohol existence
comes from fossil fuels conversion [12], where most of H2 is [46]. Nevertheless, it is observed in all these theoretical works
produced by steam reforming of natural gas [10,13]. Due to the that the size of the ambient bubble radius was fixed at a mean
environmental damage and finite life of fossil fuels, alterna- value depending on the ultrasonic conditions of irradiation
tive methods are adopted for hydrogen production such as (i.e., frequency and amplitude). However, the size of active
water electrolysis [2,14], bio-production from sludge and dairy bubbles in sono-cavitating medium is an interval rather than a
wastewater [15,16], bio-photolysis of water by algae [17], dark- single value, as demonstrated experimentally and theoreti-
fermentation hydrogen production, photo-fermentation [17], cally [47e52]. Therefore, it is expected that each bubble will be
sequential dark and photo-fermentation [17], thermolysis [2] affected differently compared to the other ones. Besides, the
and photo-electrolysis of water [2,10], gasification [4] and py- type of the adopted model may significantly affect the effect of
rolysis of biomass [2,4]. Recently, sonolysis of water have been the initial bubble size on the sono-production rate of hydrogen
successfully used for producing hydrogen [18,19]. Moreover, [53].
ultrasonication assisted hydrogen production from catalysis To the best of our knowledge, the impact of initial bubble
[20e22], photocatalysis [20e22], digestion sludge [16,23] and sizes with relation to the effect of mass transport, heat
anaerobic fermentation of wastewater [24] have proven their
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 8 7 6 7 e1 8 7 7 9 18769

exchange and chemical reactions heat on hydrogen sono- The mass flux m of evaporation and condensation at the
production is until now not investigated. Consequently, interface is expressed using Hertz-Knudsen formula derived
the present theoretical work investigates the impacts of from kinetic theory of gases [56]:
theses energetic mechanisms on range of ambient bubble
h i
sizes, for a wide range of frequency (355e1000 kHz) and rsat
g;H2 O  rg;H2 O ðRÞ


acoustic amplitude (1e3 atm). The numerical simulations m ¼ aCðTs Þ (5)
4
conducted in this paper are based on a model of a single
bubble oscillating in water under an argon atmosphere. sffiffiffiffiffiffiffiffiffiffiffiffiffiffi
8Ts Rg
CðTs Þ ¼ (6)
pMH2 O

Model where a is the evaporation coefficient (considered constant

a ¼ 0.4), CðTs Þ is the average velocity of molecules, rg,H2O (R) is
The employed model is based on a set of ordinary differential the density of water vapor in the bubble, and
equations, where the effects of non-equilibrium evaporation 3
g;H2 O ¼ 0.0173 kg m
rsat is the saturated vapor density. The
and condensation of water vapor at the bubble wall, thermal temperature of the external bubble surface is Ts ¼ Tliq.
conduction both inside and outside a bubble and chemical Heat exchange inside and outside the bubble is estimated
reactions are included. All numerical simulations have been to be [57]:
conducted for a bubble oscillating in an argon-saturated
 
water. Based on the above assumptions, temperature, pres-
Tliq  T
Q ¼ 4pR2 lmix (7)
sure, bubble radius evolution and bubble wall velocity can be Lth
determined at any instant. The radial dynamics of the bubble
( sffiffiffiffiffiffi )
is described by the modified Keller-Miksis equation (Eq. (1)), R Rc
developed by Yasui [54]: Lth ¼ min ;
(8)
p R


!

!
R m

3
2 R 2m lmix, c and Lth are the heat conductivity, thermal diffusivity
1 þ RR þ R 1  þ
C CrL 2 3C 3CrL of the gas mixture and the thickness of the thermal boundary
!

     layer, respectively.
1 R R
¼ 1þ PB ðtÞ  PA sin 2pf t þ  P∞ (1) The thermal conductivity (lmix) is estimated by [58]:
rL C C
   




!



! nH2 O nAr
mR R m m
m Rm R dPB lmix ¼ lH2 O ðTÞ þ lAr ðTÞ (9)
þ 1 þ þ Rþ þ þ nt nt
rL C CrL rL 2rL 2CrL CrL dt
where lH2O(T) and lAr(T) are the thermal conductivity of water
where dots denotes the time derivative (d/dt), R is the radius of vapor and argon at temperature T (in K), respectively. The
the bubble, C the speed of sound in the liquid, rL is the density thermal conductivity (in W m1 K1) of H2O and Ar are esti-


of the liquid, m is the net rate of evaporation per unit area and mated by [55]:
unit time and P∞ is the ambient static pressure. PA is corre-
lated with the acoustic intensity Ia (or power per unit area) as: lH20 ðTÞ ¼ 9:967213  105 T  1:1705  102 (10)
PA ¼ (2IarLC)1/2. The liquid pressure PB(t) on the external side of
the bubble wall is related to the internal pressure P(t) by the lAR ðTÞ ¼ 3:5887  105 T þ 6:81277  103 (11)
following equation [54]:
At the bubble wall, the thermal diffusivity (c) is estimated

   by [57]:
2s 4m
m
2 1 1
PB ðtÞ ¼ PðtÞ   Rþ m  (2)
R R rL rL rg lmix
c¼ (12)
Cp
where s is the surface tension, m is the liquid viscosity and rg is
the density inside the bubble. The internal pressure P(t) is where Cp is the heat capacity concentration (J m3 K1) for H2O
calculated using van der Waals equation (Eq. (3)): and Ar mixture [57]:

nRg T an2 X fi þ 2
PðtÞ ¼ þ 2 (3) Cp ¼ kB Ci NA (13)
ðV  nbÞ V 2

where a and b are the Van de Waals constants, Rg is the uni- Ci, kB, NA and fi are the molar concentration of species i (H2O
versal gas constant, V is the volume of the bubble [V¼4/3(pR3)], and Ar) inside the bubble, Boltzmann constant, Avogadro
and T is the temperature inside the bubble. The Van der Waals number and the number of degrees of freedom of species i
constants (a and b) are determined by [55]: (fH2O ¼ 6 and fAr ¼ 3), respectively.
    The temperature (T) inside bubble is calculated by solving
8 nH2 O nAr
> the following equation [54]:
< a ¼ aH2 O nt
> þ aAr
nt
    (4) ZT ZT
>
> n n an2
: b ¼ bH O H2 O þ bAr Ar
2
nt nt E ¼ nH2 O Cv;H2 O ðTÞdT þ nAr Cv;Ar ðTÞdT  (14)
V
0 0
18770 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 8 7 6 7 e1 8 7 7 9

where E is the internal energy of the bubble and CV,H2O(T) in which yki is the stoichiometric coefficient of the ith reaction
(Cv,Ar(T)) is the isochoric heat capacity of vapor (Argon) at and Xk is the chemical symbol for the kth species. The su-
temperature T, given as a polynomial approximation (ex- perscript ‘ indicates forward stoichiometric coefficients, while
pressions are available in Ref. [59]). “ indicates reverse stoichiometric coefficients. The production


The change of the internal energy of a bubble (DE) in time
rate Uk of the kth species can be written as a summation of the
(Dt), due to the pressure work, heat of chemical reactions
rate of the variables for all reactions involving the kth species:
within the bubble, energy carried by water molecules by
! !
evaporation and condensation and heat exchange by diffu-
1 dnk X
I
 00 0
sion at the interface, is expressed by [54,60]: Uk ¼ y  yki ri k ¼ 1;&; K (17)
V dt i¼1 ki
 
Dt
Tliq  T Where nk is the number of moles of the kth species. The rate ri
DE ¼  PðtÞ:DVðtÞ þ 4pR2 mCv;H2O þ 4pR2 Dtl
MH2 O Lth for the ith reaction is given as:
4 X25
 pR3 Dt i¼1 DHi ri (15) Y
K Y
K
3 0 00
ri ¼ kfi ½Xk yki  kri ½Xk yki (18)
where DHi and ri are the enthalpy change and the rate of the k¼1 k¼1

ith reaction, respectively, the first term in the right-hand side where [Xk] is the molar concentration of the kth species and kfi
of Eq. (15) is the PV work. The second term is the energy car- and kri are the forward and reverse rate constants of the ith
ried by evaporating vapor from the surrounding liquid into the reaction, respectively. The forward and reverse rate constants
bubble and by condensing vapor from the bubble into the for the ith reactions are assumed to have the following
liquid in Dt. The third term is the energy change due to the Arrhenius temperature dependence:
thermal conduction. The last term is the heat of chemical
 
reactions taking place inside the bubble during the collapse. Eafi
kfi ¼ Afi Tbfi exp  (19)
In this work, a scheme of 25 reversible chemical reactions Rg T
is considered (Table 1), in which K chemical species is
 
involved. The general form of these reversible reactions is Ea
kri ¼ Ari Tbri exp  ri (20)
given as follows: Rg T

X
K X
K where Rg is the universal gas constant, Afi (Ari) is the pre-
00
y0ki Xk 4 yki Xk (16) exponential factor, bfi (bri) is the temperature exponent and
k¼1 k¼1

Table 1 e Scheme of the possible chemical reactions inside a collapsing argon bubble [35,73]. 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 DH 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 DH
C C 23 5 22
1 H2O þ M # H þ OH þ M 1.912  10 1.83 1.185  10 2.2  10 2.0 0.0 121.72


2 OH þ M # O þ HCþM 9.88  1017 0.74 1.021  105 4.714  1018 1.0 0.0 104.36
3 O þ O þ M # O2þM 6.165  1015 0.5 0.0 4.515  1017 0.64 1.189  105 120.91
4 HCþO2 # OþCOH 1.915  1014 0.0 1.644  104 5.481  1011 0.39 2.93  102 16.54
5 HCþO2 þM # HOC 2 þM 1.475  1012 0.6 0.0 3.09  1012 0.53 4.887  104 - 49,0
6 O þ H2O # COHþCOH 2.97  106 2.02 1.34  104 1.465  105 2.11 2.904  103 17.37
7 HOC

2 þH # H2þO2 1.66  1013 0.0 8.23  102 3.164  1012 0.35 5.551  104 - 57.34
8 HOC2 þH
C
# COHþCOH 7.079  1013 0.0 2.95  102 2.027  1010 0.72 3.684  104 - 38.82
9 HO2 þO # COH þ O2
C
3.25  1013 0.0 0.0 3.252  1012 0.33 5.328  104 - 55.47
10 HOC C
2 þ OH # H2O þ O2 2.89  1013 0.0 4.97  102 5.861  1013 0.24 6.908  104 - 72.83
11 H2þM # H
þH
þM 4.577  1019 1.4 1.044  105 1.146  1020 1.68 8.2  102 106.33
12 O þ H2 # HCþCOH 3.82  1012 0.0 7.948  103 2.667  104 2.65 4.88  103 1.97
C
13 OH þ H2 # HCþH2O 2.16  108 1.52 3.45  103 2.298  109 1.40 1.832  104 - 15.4
14 H2O2þO2 # HO22þHOC 2 4.634  1016 0.35 5.067  104 4.2  1014 0.0 1.198  104 41.95
15 H2O2þM # COHþCOH þ M 2.951  1014 0.0 4.843  104 1.0  1014 0.37 0.0 52.13
16 H2O2þHC # H2OþCOH 2.410  1013 0.0 3.97  103 1.269  108 1.31 7.141  104 - 69.6
17 H2O2þHC # H2þHOC 2 6.025  1013 0.0 7.95  103 1.041  1011 0.70 2.395  104 - 15.38
18 H2O2þO # COH þ HOC 2 9.550  106 2.0 3.97  103 8.66  103 2.68 1.856  104 - 13.42
19 H2O2þCOH # H2O þ HOC 2 1.0  1012 0.0 0.0 1.838  1010 0.59 3.089  104 - 30.78
20 O3þM # O2þO þ M 2.48  1020 0 2.27  104 e e e 26.14
21 O3þO # O2þO2 5.2  1018 0 4.157  103 e e e - 94.77
22 O3þ
OH # O2þ HO
2 7.8  1017 0 1.9  103 e e e - 39.46
23 O3þ HOC C
2 # O2þO2þ OH 1  1017 0 2.8  103 e e e - 29.17
24 HCþ O3 # HOC 2 þO 9  1018 0.5 3.99  103 e e e 32.45
25 HCþ O3 # COH þ O2 1.6  1019 0 0 e e e - 23.01
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 8 7 6 7 e1 8 7 7 9 18771

Efi (Eri) is the activation energy. Arrhenius parameters of each

3. Model without mass transfer (i.e. denoted as m ¼ 0),
chemical reaction are presented in Table 1. 4. Model without reactions heats (i.e. denoted as DH ¼ 0).
The water vapor change with time inside the bubble, due to
the evaporation and condensation at the bubble wall and due
to chemical reactions is given by: Total production rates


m

nH2 O ðt þ DtÞ ¼ nH2 O ðtÞ þ 4pR2 Dt þ VDtUH2 O (21) Fig. 1 shows the effect of frequency (355, 500 and 1000 kHz)
MH2O
and acoustic amplitude (1.5e3 atm) on the total production
For other species k (except Ar): rate of all species created inside the bubble at the end of the
bubble collapse, i.e. COH, HC, O, HOC 2 , H2, O2 and H2O2, for the


nk ðt þ DtÞ ¼ nk ðtÞ þ VDtUk (22) four treated scenarios: normal model, model without heat
transfer, model without mass transfer and model without
The modified Keller-Miksis equation (Eq. (1)), is a nonlinear
reactions heat. The calculations are given for ambient bubble
second-order differential equation, which can be reduced to a
radii that provide the maximum response (production rate),
system of two differential first-order equations as
which are given in the following section (Production rate of
dR
hydrogen). The total production rate is the total amount of
¼R (23)
dt the created species inside the bubble at the end of the first
bubble collapse multiplied by the corresponding driving fre-
8
!    



! 9
1 R R mR R m quency [30,34,42]. The selected range of ultrasound frequency
>
> PB ðtÞPA sin 2pf tþ P∞ þ 1 þ þ>
>
>
> 1þ >
> (355, 500 and 1000 kHz) is based on many experimental works,
< rL C C rL C CrL =
which found that the best frequency for sonochemistry is
>

!

! >
>
>



m
m Rm R dPB 3
2 >
>
>
: R 2m >
; ranged from 300 to 1000 kHz [61e70]. These work confirmed

Rþ þ þ R 1 þ
dR rL 2rL 2CrL CrL dt 2 3C 3CrL that lower frequencies (i.e., usually 20 kHz) is not suitable for
¼ !
dt

producing efficient sonochemical effects in aqueous solution.
1 CR þ CrmL R However, some numerical simulation of hydrogen production
at lower frequencies (for single bubble scale) has already been
(24)
given in our previous work [32]. The acoustic intensity In
Equations (14), (23) and (24) are solved using finite differ- corresponding to the three used acoustic amplitudes, PA ¼ 1.5,
ence method. The outputs of these equations are the bubble 2 and 3 atm, are respectively, 0.781, 1.4 and 3.13 W/cm2, as
wall velocity, evolution of the bubble radius, variation of calculated from the equation relying PA with In (i.e., PA ¼
bubble temperature and pressure all along the bubble oscil- (2IarLC)1/2, which is given in section Model, just after Eq. (1)).
lation, respectively. The variation in time of number of moles The acoustic energies (i.e., In  S) required for delivering theses
of each species housed within the bubble is given by Equations intensives depends on the area “S” of the irradiating trans-
(21) and (22). The amount of argon remains unchanged during ducer. For example, if the diameter of the transducer is equal
the bubble oscillation (i.e. chemically inert). to 5 cm, the acoustic energies could be then 15.3, 27.5 and
61.4 W, for PA ¼ 1.5, 2 and 3 atm, respectively.
The total production rates increase when the acoustic
Results and discussion amplitude is raised or if the ultrasound frequency is lowered.
For example, the total maximal production rate reached by
It should be noted here that only the case of a single bubble the model without reactions heat at an acoustic amplitude of
cavitation is taken into account, where the different in- 1.5 atm is 1.59  1011 mol s1 under the ultrasonic frequency
teractions between bubbles in the sonicated liquid are of 355 kHz. This yield goes up to 7.6  1011 mol s1 for PA-
ignored. Additionally, all simulations were conducted for ¼ 2 atm, and increases up to 3  1010 mol s1 under PA-
argon-saturated water at 20  C. Therfore, the initial bubble ¼ 3 atm, for the same frequency. On the other hand, the
content is a mixture of water vapor and argon. The complete maximal rates of production are obtained when the model
bubble-dynamics model includes the liquid compressibility without thermal conduction is used (Fig. 1), this confirms the
and viscosity, heat transfer (i.e. thermal conduction through importance of the heat transfer into the bubble internal en-
bubble wall), mass transfer (i.e. nonequilibrium condensation ergy balance. The production rates obtained through the
and evaporation of the liquid vapor across the bubble/liquid model without reactions heat persist to be greater than those
interface), reaction kinetics occurring inside the bubble (i.e. retrieved for the normal model (Fig. 1). However, the model
reactions heats are incorporated). In the purpose to evaluate without mass transport gives the lowest production rates
the effects of different parameters injected into the energy even after raising the acoustic amplitude from 2 atm to 3 atm
equation of a single bubble, we will assess in the next sections (Fig. 1), where the maximal temperatures retrieved for this
the result of elimination of each of these parameters on H2 model (without mass transport) can exceed those given by the
production. The investigated cases are: other models. This is due to the elimination of the nonequi-
librium evaporation and condensation for this model. It
1. Complete model with including all parameters (i.e. deno- should be noted that the increase of all the total production
ted as normal), rates (for all models with the exception of the model without


2. Model without heat transfer (i.e. denoted as Q ¼ 0), mass transport) is proportional to the maximal temperatures
18772 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 8 7 6 7 e1 8 7 7 9

Fig. 1 e The total production rates of all species inside the bubble, excepting argon, as function of the acoustic amplitudes
(1.5, 2 and 3 atm) and the ultrasound frequencies (355, 500 and 1000 kHz) for the different models. The vertical axis is in
logarithmic scale. Calulations are made for R0's of the maximum responses, corresponding to the maximum production
rates.

reached at the end of collapse (the temperature profiles will be bubble sizes. This is due to the fact that when the acoustic
given in the following sections). power is raised, the water vapor entering the bubble during
the rarefaction phase will be huge, which means obviously a
Production rate of hydrogen soft collapse. These behaviors are observed for all the used
frequencies. The same trend is found experimentally by
In Fig. 2(a)-(i), the production rate of hydrogen is calculated on Brotchie et al. [52] and theoretically by Yasui et al. [42] for
a range of ambient bubble sizes for various frequencies (355, sonoluminescing and sonochemically active bubbles. In
500 and 1000 kHz) and different acoustic amplitudes (from 1.5 addition, it is observed that the wave frequency rise or the
to 3 atm). Data of Fig. 2(a)e(i) are given for the different acoustic amplitude decrease cause the range of active bubbles
investigated models (i.e. complete model, model without heat to be narrowed.
condition, model without mass transfer and model ignoring For PA ¼ 1.5 atm, Fig. 2(a)e(c), the energetic weightiness of
reactions heat). The production rate of hydrogen is defined as the model without thermal conduction is quite obvious for all
the amount of H2 created inside the bubble at the end of the the ultrasonic frequencies. The maximal production rates
first bubble collapse multiplied by the driving frequency retrieved for this model at the optimum bubble radii are
[30,42]. 1.5  1014 mol s1 for 355 kHz (R0 ¼ 3 mm), 6.2  1018 mol s1
According to Fig. 2(a)e(i), the rate of hydrogen production is for 500 kHz (R0 ¼ 2.5 mm) and 1.13  1026 mol s1 for 1000 kHz
increased with the decrease of the ultrasound frequency or if (R0 ¼ 2 mm). In spite of the elimination of non-equilibrium
the acoustic power is increased. However, from a certain evaporation and condensation for the model without mass
acoustical conditions and depending on the eliminated ener- transport, the maximal production rate of H2 in this case is
getic mechanism this increase is amortized. On the other found to be greater than those found by using either the model
hand, it is clear that for all the used frequencies (355, 500 and without reactions heat or the normal model (Fig. 2(a)e(c)). The
1000 kHz), the maximal response (maximal production rate) is maximal production rates of H2 for the model without mass
shifted toward smaller ambient bubble radii when the transport at the ultrasound frequencies of 355 kHz (R0 ¼ 3 mm),
acoustic amplitude is increased or if the ultrasound frequency 500 kHz (R0 ¼ 2.5 mm) and 1000 kHz (R0 ¼ 2 mm) are
is raised. This is because when the ultrasonic frequency is 1.27  1014 mol s1, 2.88  1018 and 2.45  1029 mol s1,
increased, bubbles are found to be enable to largely expand so respectively. For the model without reactions heat or the
that the maximal response is automatically shifted toward normal model under the ultrasound frequencies of 500 and
smaller bubble radii [34,42]. Conversely to the case when the 100 kHz (PA ¼ 1.5 atm), the maximal production rates of H2 are
ultrasonic frequency is reduced, bubbles will get more time to the same, with the exception of the ultrasound frequency of
expand, therefore expansion and compression ratios are 355 kHz, where the effect of the eliminated reactions heat
higher in this case, and the maximal response is moved to- promotes more the increase of the internal energy of bubble
ward larger bubble radii. On the other hand, when the ultra- compared to the normal model. This is due to the fact that for
sonic frequency is fixed, the increase of the acoustic the normal model the endothermic reactions involved into the
amplitude shows a negative influence on the larger ambient kinetic mechanism (Table 1) participate to reduce largely the
bubble radii, causing the shifting of the maximal response temperature increase inside the bubble during the collapse, as
(maximal production rate) toward lower values of ambient it is found by many researchers [29,59,71]. It should be noted
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 8 7 6 7 e1 8 7 7 9 18773

Fig. 2 e Production rate of H2 as a function of ambient bubble radius (R0) under varoius frequencies and acoustic amplitude,
for models without mass transfer, without heat transfer, without reactions heat and complete model (normal).

here that the superior rate of H2 production obtained by the it is shown in Fig. 3(a)e(c) (i.e. case of PA ¼ 1.5 atm). On the
model without mass transport (for all frequencies) compared other hand, for the ultrasound frequencies of 355 Hz and
to either the model without reactions heat or the normal 500 kHz (PA ¼ 2 atm), a lower increase is registered for the
model is due to (i) the weak acoustic power applied for all the maximal H2 yield for the model without mass transport
models (PA ¼ 1.5 atm), so that the increase of temperature in compared to that found by using the model without reactions
this case is insufficient to reveal the effect of the reactions heat or the normal model. However, for the ultrasonic fre-
heat elimination or the consideration of all the energetic quency of 1000 kHz (Fig. 2(f)), the maximal production rate
mechanisms (normal model) and (ii) the elimination of water retrieved for the model without mass transport is greater than
condensation during the compression phase for the model that of the model without reactions heat or the normal model.
without mass transfer. The average temperatures obtained at This is obviously explained as in the previous paragraph,
the maximal response (PA ¼ 1.5 atm) for each of the used especially where the average of the maximal temperatures
frequencies are around 3500, 2500 and 1300 K for 355, 500 and attained for all the used models in this case (PA ¼ 2 atm,
1000 kHz, respectively (Fig. 3(a)-(c)). f ¼ 1000 kHz) is around ~ 3000 K. As it is expected, the increase
For PA ¼ 2 atm, Fig. 2(d)e(f), the important impact of the of the acoustic power promotes more the effect of the re-
thermal conduction mechanism within the bubble internal actions heat elimination compared to the case of the normal
energy balance persist to be dominant, where the maximal model. This is translated by the increase of the maximal H2
production rates of H2 found under 355 kHz (R0,opt ¼ 2.1 mm), production rate for the model without reactions heat
500 kHz (R0,opt ¼ 1.7 mm) and 1000 kHz (R0,opt ¼ 1.5 mm) are (3.6  1011 mol s1 for PA ¼ 2 atm and 4.26  1015 mol s1 for
5  1011, 1.28  1011 and 4.92  1017 mol s1, respectively. PA ¼ 1.5 atm) in comparison to the normal model
The adoption of the thermal model used by T€ogel [72] imply (3  1011 mol s1 for PA ¼ 2 atm and 2.5  1015 mol s1 for
that the increase of the bubble temperature will be significant PA ¼ 1.5 atm) for the frequency of 355 kHz (Fig. 2(a) and (d)).
compared to the normal model, where the lost energy is By increasing the acoustic amplitude to 3 atm under the
important because of the constant temperature considered on ultrasound frequency of 1000 kHz (Fig. 2(i)), the maximal
the external bubble wall. At the opposite, in this case (PA- production rate (at R0 ¼ 1.3 mm) of H2 (for all models) is raised
¼ 2 atm), the differences between the maximal temperatures to an appreciable amount compared to its value for the case
(for the all the adopted models at around R0 of maximal when the acoustic amplitude is 2 atm for the same wave fre-
response) reached for each of the used frequencies are clear as quency. This is logically interpreted by the maximal
18774 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 8 7 6 7 e1 8 7 7 9

500 kHz (Fig. 2(g) and (h)), it seems that the maximal increase
of the hydrogen production rate is amortized compared to the
case of 1000 kHz under always the same acoustic amplitude of
3 atm (Fig. 2(d)e(i)). For example, for the model without ther-
mal conduction, the maximal ratio of increase of H2 produc-
tion rate is 1.42 passing from an acoustic amplitude of
2 atme3 atm under the ultrasound frequency of 355 kHz
(Fig. 2(d) and (g)). This maximal ratio decreases to 1.25 for the
ultrasonic frequency of 500 kHz (Fig. 2(e) and (h)). This in-
dicates the existence of a plateau for the maximal production
of hydrogen with respect to PA. To explain this, we should take
into account the kinetic constants of the main reactions tak-
ing place into the bubble during collapse and the temperature
profiles evolving inside bubble. According to Fig. 3(a) and (b)
and , we observe that at PA ¼ 3 atm for the ultrasonic fre-
quencies of 355 kHz and 500 kHz, the picks temperatures of all
models are around or greater than 10,000 K, especially for the
model without thermal conduction or the model without
mass transport. This increase of temperature is owing to the
raise of acoustic intensity, where the acceleration of bubble
wall during the collapse phase generates a violent collapse at
the end of compression period. Consequently, the general
production of bubble is improved. The increase of bubble
temperature is a frequency and mechanism (mass, heat and
chemical reaction) dependent. This huge temperatures
developed within bubbles, promotes the thermal dissociation
of water molecules as well as COH radicals as seen in Fig. 4(a)
and (b) (1st and 2nd reactions of Table 1). Consequently,
important amounts of COH, O and HC radicals are formed.
However, the formation of O2 molecules seems to be clearly
lowered because of the higher backward reaction constant at
around or greater than 10,000 K (Fig. 4(c)). On the other hand,
Fig. 4(d) indicates the increase of O radicals consumption
especially due to the water molecules found inside bubbles
and the relatively higher forward constant. According to the
11th reaction (Table 1 and Fig. 4(e)), the consumption of H2
goes up rapidly especially for higher temperatures (around
Fig. 3 e The maximal temperatures attained at R0 of the and greater 10,000 K), this is clearly shown by the forward and
maximal response for the different models as a function of backward constants. At the opposite, the hydrogen con-
the acoustic amplitude (1.5, 2 and 3 atm) and the sumption is reduced as it is shown in Fig. 4(f) according to the
ultrasound frequency (355, 500 and 1000 kHz). 12th reaction of Table 1, where the backward constant is
relatively greater than the forward constant, and also due to
the large HC and COH radicals created within the bubble. It
temperatures retrieved for each of the used models (Fig. 3(c)). should be noted here that according to the theoretical study of
The picks temperatures developed inside the bubble at Merouani et al. [35], it has been shown that the 12th reaction is
collapse for PA ¼ 3 atm and f ¼ 1000 kHz using the model the main reaction responsible of the hydrogen production
without thermal conduction, mass transport, reactions heat inside the bubble (gas phase). Taking into account the 11th
and the normal model are 11,080 K, 9030 K, 8340 K and and 12th reactions of Table 1 and Fig. 4(e) and (f), we can
71,340 K, respectively (Fig. 3(c)). It should be noted that in spite conclude that at higher temperatures (around and greater
of the maximal temperature attained using the model without than 10,000 K, Fig. 3(a)e(c)), the consumption of H2 is slightly
mass transport (9030 K) at this acoustic amplitude and fre- promoted (for all the used models), this explain the existence
quency (3 atm, 1000 kHz), the maximal production rate of H2 of a plateau for the hydrogen production rate [Fig. 2(d) and (e),
retrieved for this model is the lowest one compared to the rest Fig. 2(g) and 2(h)]. Some exception is indicated at the acoustic
models, which is explained especially by the ignored water amplitude of 3 atm (Fig. 2(g)) for the model without mass
molecules evaporation during the expansion phase. On the transport, where the maximal response (maximal production
other hand, for the ultrasound frequencies of 355 kHz and rate) is moved toward R0 ¼ 0.5 mm.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 8 7 6 7 e1 8 7 7 9 18775

Fig. 4 e Evolutions vs. temprature of the forward and reverse rate constants of reactions 1, 2, 3, 6, 11 and 12 of Table 1. Units:
cm3 mol¡1 s¡1 for kf1, kf2, kf6, kr6, kf1, kf12 and kr12, and cm6 mol¡2 s¡1 for kr1, kr2 and kr11.

maximal response (maximal production rate) is shifted to-

Conclusion ward lower values when the ultrasound frequency (for a
constant amplitude) or the acoustic amplitude (for a constant
In this work, numerical simulations have been performed to frequency) is raised. In addition, it is observed that the in-
visualize the effect of each of the energetic mechanisms crease of wave frequency or the decrease of acoustic ampli-
(thermal conduction, mass transport, reactions heat) involved tude cause the range of active bubbles to be narrowed.
into the bubble internal energy balance on the sono- Besides, the great importance of the thermal conduction and
production rate of hydrogen. These computer simulations the reactions heat has been demonstrated inside the bubble
have revealed the existence of a plateau for the hydrogen internal energy balance as they are compared to the case of
production rate (especially at around R0 of the maximal the normal model. Moreover, the mechanism of mass trans-
response, for all models), conversely to the total yield where port has a clear impact in this energetic balance, especially
no optimum is registered for this case. This was explained by this effect is important in term of total production rates.
the effect of temperature profiles on the main reactions Unfortunately, the results of this study could not be related
involving H2 (taking into account their kinetic constants). to the experimental studies of hydrogen production available
These observations reveal the possibility of an economical in the literature because the available experimental data were
production of hydrogen without using higher acoustic powers, obtained in aqueous solution (i.e., multibubble system/
with respect to the wave frequency. On the other hand, it was macroscopic scale), whereas our findings were obtained from
shown that in general, the production rates are increased a single bubble (microscopic scale). For passing from a single
either by the decrease of the wave frequency or the increase of bubble scale to multibubble system, we need the determina-
the acoustic power. The ambient bubble size (R0) of the tion of the number of cavitation bubbles as well as the
18776 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 8 7 6 7 e1 8 7 7 9

interactions between bubbles in the aqueous system (phe- pmax Maximum pressure inside the bubble, (Pa)
nomenon ignored in our study). The determination of these p∞ Ambient static pressure, (Pa)
two last parameters is very difficult, if not impossible, due to PA Amplitude of the acoustic pressure, (Pa)
the chaotic nature of acoustic cavitation. Pv Vapor pressure of water, (Pa)
Finally, a debate has been recently opened about the effect R Radius of the bubble, (m)
of saturation gases on the acoustic generation of hydrogen. Rmax Maximum radius of the bubble, (m)
The type of the saturation gases affects significantly the R0 Ambient bubble radius, (m)
chemistry inside the bubble owing to the gas characteristics Rg Ideal gas constant, (J/mol K)
(i.e., thermal conductivity and specific heat capacities, Cp and t Time, (s)
Cv) which enter directly in equations governing the bubble T Temperature inside the bubble, (K)
dynamics (see Eqs. (7), (8) and (14)) as well as the bubble Tmax Maximum temperature inside the bubble, (K)
chemistry (for diatomic and polyatomic gases only, i.e. O2, N2, T∞ Bulk liquid temperature, (K)
CO2, air, …, because monoatomic gases are inert). Addition- x Thermal diffusivity inside the bubble, (m2 s1)
ally, the selection of the right initial conditions (especially, the Cp Heat capacity concentration inside the bubble, (J m3
initial bubble radius and the acoustic amplitude) for each K1)
frequency and gas is of crucial role in determining if these MH2O Molar mass of water, (kg mol1)
bubbles are chemically active (inertial bubbles) or not (dis- m Evaporation-condensation rate of water, (kg m2 s1)
solving or degasing bubbles). All these issues related to the Q Energy transferred by heat exchange, (J s1)
type of saturation gases will be treated in detail in future paper n Molar amount, (mol)
which will investigate the gas atmosphere impacts on the PB Liquid pressure on the external side of the bubble
chemical activity and the size of active bubbles by adopting wall, (Pa)
the same strategy of the present paper (i.e., using different V Volume of the bubble, (m3)
models).
Greek letters
s Surface tension of liquid water, (N m1)
rl Density of liquid water, (kg m3)
Declaration of competing interest
rg Density inside the bubble, (kg m3)
lmix Thermal conductivity of the mixture, (W m1 K1)
The authors declare that they have no known competing
li Thermal conductivity of species i, (W m1 K1)
financial interests or personal relationships that could have
m Dynamic viscosity, (Pa s)
appeared to influence the work reported in this paper.
a Accommodation coefficient
rH2O Density of water vapor inside the bubble, (kg m3)
rsat,H2O Saturated vapor density (kg m3)
Acknowledgements yki Stoichiometric coefficient of the kth chemical
species in the ith reaction


This study was supported by The Ministry of Higher Education Uk Production rate of the kth species, (mol s1 m3)
and Scientific Research of Algeria (project No.
A16N01UN250320180001) and the General Directorate of Sci-
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