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Chemical Engineering Journal 426 (2021) 130251
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Chemical Engineering Journal

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Effect of carbon tetrachloride (CCl4) sonochemistry on the size of active

bubbles for the production of reactive oxygen and chlorine species in
acoustic cavitation field
Aissa Dehane a, Slimane Merouani b, *, Oualid Hamdaoui c
a
Laboratory of Environmental Engineering, Department of Process Engineering, Faculty of Engineering, Badji Mokhtar – Annaba University, P.O. Box 12, Annaba 23000,
Algeria
b
Laboratory of Environmental Process Engineering, Department of Chemical Engineering, Faculty of Process Engineering, University Salah Boubnider-Constantine 3, P.O.
Box 72, Constantine 25000, Algeria
c
Chemical Engineering Department, College of Engineering, King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia
A R T I C L E I N F O A B S T R A C T
Keywords: It is known that the evaporation of carbon tetrachloride (CCl4) into the acoustic cavitation during water sonolysis
Sonochemistry results in the generation of many reactive species (e.g. chlorinated elements), probable reduction of bubble
Carbon tetrachloride (CCl4) temperature and the scavenging of hydrogen atom by its reaction with CCl4. Consequently, the chemistry of
Sono-activity
bubbles (sono-activity) is completely modified, which means that the change of the active bubbles distribution is
Bubble size
more plausible in the presence of CCl4. The present work gives the first study of the impacts of carbon tetra
Frequency
Acoustic intensity chloride on the size distribution of active bubbles as well as the optimum size for the maximal yielding of reactive
oxygen species (ROS: ●OH, O, O3, HO● 2 and H2O2) and reactive chlorine species (RCS: CCl3, :CCl2, Cl, Cl2,
● ●
HOCl). In addition, the extent of these effects (of carbon tetrachloride) was evaluated as function of the ultra
sonic parameters, namely, ultrasound frequency and acoustic intensity. It has been shown that the optimum
ambient bubble radius for the maximal production of ROS and RCS shifts towards higher values (~6–7 µm) when
CCl4 concentration is greater than 0.02 mM (i.e. for a frequency of 300 kHz). However, for lower concentrations
of CCl4 (<0.02 mM), this optimum exists at around 3.1 µm. As the acoustic intensity is raised, the range of active
bubbles and the optimum size are increased, where this effect is more intense for CCl4 concentrations greater
than ~0.01 mM. For higher frequencies, 875 and 1000 kHz, it has been demonstrated that the existence of CCl4
in the bulk liquid practically has no effect on the optimum size for the maximal yielding of oxidants.
●
OH, HO● 2 and H ) and reactive species (e.g., H2O2) of great importance
●
1. Introduction are created by the thermal decomposition of vapor and gases found in
the bubble [11,12]. Sonication has been efficiently used for the degra
The ultrasonic irradiation (sonication) of solutions is considered as dation of wide range of organic contaminants [1,2,9,13–15]. Compared
one of the important techniques of advanced oxidation processes (AOPs) to other advanced oxidation techniques, sonolysis has the advantage of
for the degradation of hazardous organic contaminates in water [1]. coupling two degradation pathways: (i) pyrolysis inside the bubble (for
Water sonolysis generates acoustic cavitation, that is defined as the volatile compounds) and (ii) reaction with free radicals, mainly ●OH, at
formation, growth and collapse of microbubbles, which is the main the bubble/solution interface and in the liquid bulk for nonvolatile
event responsible for all physical and chemical aspects of ultrasound in pollutants (of hydrophobic or hydrophilic character) [14]. However, it
aqueous solution (e.g., degassing, cleaning, production of reactive free has been found that the rate of degradation is rather slow for practical
radicals, sonoluminescence and shock waves) [2–4]. All these resulted application, especially for nonvolatile pollutants [16].
events are due to the generation of suitable conditions (temperature Carbon tetrachloride is one of the organic pollutants found in
~5000 K and pressure ~1000 atm [5–7]) for the sonolysis of water groundwater and river water. The consumption of CCl4 causes serious
vapor and volatile species present inside the acoustic cavitation at the problems for liver, kidney, brain and pulmonary system [17,18].
strong collapse [8–10]. Consequently, several reactive radicals (e.g., Consequently, the sonolysis of CCl4 has been found to be a promising
* Corresponding author.
E-mail addresses: [email protected], [email protected] (S. Merouani).
https://doi.org/10.1016/j.cej.2021.130251
Received 19 February 2021; Received in revised form 27 April 2021; Accepted 4 May 2021
Available online 14 May 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
A. Dehane et al. Chemical Engineering Journal 426 (2021) 130251
Nomenclature Tmax Maximum temperature inside a bubble, (K).

T∞ Bulk liquid temperature, (K).
Af (Ar) Pre-exponential factor of the forward (reverse) reaction, x Thermal diffusivity inside the bubble, (m2/s)
[(cm3 mol− 1 s− 1) for two body reaction and (cm6 mol− 2 Cp Heat capacity concentration inside the bubble, (J/m3 K)
s− 1) for three body reaction]. MH2O Molar mass of water, (kg/mol).
bf (br) Temperature exponent of the forward (reverse) reaction. ṁ Evaporation-condensation rate of water, (kg/m2 s).
c Speed of sound in the liquid medium, (m s− 1). Q Energy transferred by heat exchange, (J/s)
Eaf (Ear) Activation energy of the forward (reverse) reaction, (cal n Molar amount, (mol).
mol− 1). PB Liquid pressure on the external side of the bubble wall,
f Frequency of ultrasonic wave, (Hz). (Pa).
Ia Acoustic intensity of ultrasonic irradiation, (W m− 2). V Volume of the bubble, (m3).
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]. σ Surface tension of liquid water, (N m− 1).
p Pressure inside a bubble, (Pa). ρl Density of liquid water, (kg m− 3).
pmax Maximum pressure inside a bubble (Pa). ρg Density inside the bubble, (kg m− 3).
p∞ Ambient static pressure, (Pa). λmix Thermal conductivity of the mixture, (W m− 1 K).
PA Amplitude of the acoustic pressure, (Pa). λi Thermal conductivity of species i, (W m− 1 K).
Pv Vapor pressure of water, (Pa). µ Dynamic viscosity, (Pa s).
R Radius of the bubble, (m). α Accommodation coefficient.
Rmax Maximum radius of the bubble, (m). ρH2O Density of water vapor inside the bubble, (kg/m3).
R0 Ambient bubble radius, (m). ρsat,H2O Saturated vapor density, (kg/m3).
Rg Ideal gas constant (J/mol K). υki Stoichiometric coefficient of the kth chemical species in the
t Time, (s). ith reaction.
T Temperature inside a bubble, (K). U̇k Production rate of the kth species, (mol/s m3).
method for an efficient elimination of this substance [8–10,19–22]. bubbles population has a great importance, because if this range is
Much efforts have been devoted in order to enhance the eliminationof accurately determined, it will be easy to study the effects produced by
CCl4, where a variety of experimental conditons has been investi these bubbles and their interactions with the ultrasonic irradiation [40].
gated, e.g. ultrasound frequency [8,9,21,23,24], acoustic intensity This parameter has been determined experimentally and theoretically by
[20,25–27], initial CCl4 concentration [10,18,26], bulk solution many researchers but only for pure (i.e., deionized) water [37,38,41–47],
temperature [20,25,26,28], saturation gases [25], presence of other and there was no previous work investigating the impact of CCl4 evapo
contaminant [18,19], variation of static pressure [29] and pH of so ration and sono-pyrolysis on the size of active bubbles in sonochemical
lution [26]. In general, it was found that the ultrasonic degradation of reaction field.
CCl4 is very efficient even when no additive is used. This is due to its In the present study, the impact of CCl4 concentration (in solution)
high volatility, which means that carbon tetrachloride is rapidely on the range of ambient bubble radius for sonochemically active bubbles
pyrolysed inside the bubble at collapse [21]. On the other hand, is revealed for the first time, where a reaction mechanism of CCl4 sono-
because carbon tetrachloride is considered as a good scavenger of pyrolysis is used. In addition, these effects of CCl4 concentration are
hydrogen atom (k = 3.8 × 107 M− 1 s− 1 [30]) and its pyrolysis can analyzed for a range of ultrasonic frequency (213–1000 kHz) and
generate reactive chlorine species (RCS), many research studies have acoustic intensity (0.7–1.5 W/cm2). All these issues were treated on the
focused on the use of CCl4 for improving the sonochemical degrada basis of a single bubble sonochemistry for CCl4 in medium (water)
tion of different nonvolatile contaminants (e.g. dyes [31,32], phenolic saturated with argon.
compounds [33,34], ciprofloxacin [35] and levofloxacin [36]). This
improving aspect of CCl4 toward nonvolatile substrates has been 2. Theoretical package
analyzed over a wide range of conditions like the initial dosage of
CCl4 [10,18,26], the wave frequency [8,9,21,23,24], power (acoustic 2.1. Model
intensity) [20,25–27], the solution temperature [20,25,26,28], the
type of saturation gases [25], the static pressure [29] and the solution The physical situation of the model is that of an isolated gas
pH [26]. and vapors (water and CCl4) filled spherical bubble oscillating in
However, in spite of the great number of experimental works found in compressible water under the action of a sinusoidal sound wave, where
literature, the mechanism of CCl4 decomposition within the bubble is not the effects of non-equilibrium evaporation and condensation of water
well understood. This is owing to the complicate mechanism of CCl4 vapor at the bubble wall, thermal conduction both inside and outside a
decomposition inside the bubble as well as the strong dependence of the bubble and chemical reactions are included. Numerical simulations
pyrolytic pathway to the used processing conditions (particularly, fre have been conducted for a bubble oscillating in an argon-saturated
quency, acoustic power and the type of saturation gas). More interest water containing different concentrations of carbon tetrachloride.
ingly, the endothermal dissociation of CCl4 within the bubble is able to Based on the above assumptions, evolutions of temperature, pressure,
modify one of the most important characteristics of cavitation field, which bubble radius, bubble wall velocity and the chemical bubble yield can
is its ambient bubble size (R0). The extreme temperature reached inside be determined at any instant. The radial dynamics of the bubble is
the bubble and the chemical bubble yield are both strongly affected by described by the modified Keller-Miksis equation (Eq. (1)), developed
this parameter (i.e., R0) [37–39]. Consequently, it is more probable that by Yasui [48]:
the presence of CCl4 in solution modifies the size distribution of active
bubbles (in term of ambient bubble radius, R0) as well as the optimum R0
for the maximal production of oxidants. The determination of active
2
( ) ( )
Ṙ ṁ 3 2 Ṙ 2ṁ The thermal conductivity (λmix) is estimated by [53]:
1− + RR̈ + Ṙ 1 − + ( ) ( ) ( )
C C ρL 2 3C 3CρL nH2 O nAr nCCl4
( )[ ( ( )) ] ( λmix = λH2 O (T) + λAr (T) + λCCl4 (T) (9)
1 Ṙ R m̈R Ṙ nt nt nt
= 1+ PB (t) − PA sin 2πf t + − P∞ + 1−
ρL C C ρL C Where λH2O(T), λAr(T) and λCCl4(T) are the thermal conductivity of
) ( ) water vapor, argon and carbon tetrachloride at temperature T (in K),
ṁ ṁ ṁ Ṙṁ R dPB
+ + Ṙ + + + (1) respectively. The thermal conductivity (in W/m K) of H2O, Ar and CCl4
CρL ρL 2ρL 2CρL CρL dt
are estimated by [49,54]:
where dots denotes the time derivative (d/dt), R is the radius of the λH2O (T) = 9.967213 × 10− 5 T − 1.1705 × 10− 2
(10)
bubble, C the speed of sound in the liquid, ρL is the density of the liquid,
m is the net rate of evaporation per unit area and unit time and P∞ is the
∙
λAr (T) = 3.5887 × 10− 5 T + 6.81277 × 10− 3
(11)
ambient static pressure. PA is correlated with the acoustic intensity Ia (or
power per unit area) as: PA= (2IaρL C)1/2. The liquid pressure PB(t) on the λCCl4 (T) = 3 × 10− 5 T + 2.2 × 10− 3
(12)
external side of the bubble wall is related to the internal pressure P(t) by
At the bubble wall, the thermal diffusivity (χ ) is estimated by [52]:
the following Eq. [49]:
λmix
2σ 4μṘ χ= (13)
PB (t) = P(t) − − (2) Cp
R R
3
where Cp is the heat capacity concentration (J m− K− 1) for H2O,
where σ is the surface tension, µ is the liquid viscosity. P(t) is
CCl4 and Ar mixture [52]:
calculated using Van der Waals equation (Eq. (3)):
∑ fi + 2
nRg T an2 Cp = k B Ci NA (14)
P(t) = + 2 (3) 2
V − nb V
Ci, kB, NA and fi are, respectively, the molar concentration of species i
where a and b are the Van de Waals constants, Rg is the universal gas
(H2O, Ar or CCl4) inside the bubble, Boltzmann constant, Avogadro
constant, V is the volume of the bubble [V = 4/3(πR3)], and T is the
number and the number of degrees of freedom of species i (fH2O = 6, fAr
temperature inside the bubble. The Van der Waals constants (a and b)
= 3 and fCCl4 = 9), respectively.
are determined by [49]:
The temperature (T) inside the bubble is calculated by solving the
⎧ ( ) ( ) ( )
⎪ n H2 O nAr nCCl4 following Equation [55]:
⎪
⎨ a = aH2 O nt
⎪ + aAr
nt
+ aCCl4
nt ( )
( ) ( ) ( ) (4) E + anV
2
⎪
⎪ n n n
⎪ H O Ar CCl
(15)
2 4
⎩ b = bH2 O + bAr + bCCl4 T=
nt nt nt Cv nt
The mass flux ṁ of evaporation and condensation at the interface is where E is the internal energy of the bubble, nt is the total number of
expressed using Hertz-Knudsen formula derived from kinetic theory of moles inside the bubble, V is the bubble volume and Cv is the molar heat
gases [50]: of gases and vapor within the bubble. For monoatomic gases (Ar, He,…),
the molar heat is (3/2)Rg, for diatomic gases (H2, O2, …), it is (5/2)Rg,
{Psat [R] − Pv }
ṁ = a √̅̅̅̅̅̅̅̅̅̅̅̅
2π T[R] Rg
(5) for the other gases, it is (6/2)Rg.
MH2 O In this work, the change of the internal energy of a bubble (ΔE) in
time (Δt), due to the pressure work, heat of chemical reactions within
where Psat[R] is the saturated vapor pressure (calculated by using
the bubble, energy carried by water molecules by evaporation and
Antoine’s equation) at the interface temperature T[R] = Tliq, Pv is the
condensation and heat exchange by diffusion at the interface, is
vapor pressure within the bubble, MH2O is the molecular weight of water
expressed by [55,56]:
vapor and ‘a’ is the accommodation coefficient, given as [51]:
⎧
⎪
⎪ a = 0.35, for T⩽350 K
⎪
⎪ ( )2 ( )( )( )
⎨ T
T T T
a = 0.35 − 0.05 − 7 + 0.025 − 7 − 8 − 9 , for 350⩽T⩽500K (6)
⎪
⎪ 50 50 50 50
⎪
⎪
⎩
a = 0.05, for T⩾500 K
( )
ṁ Tliq − T 4
Heat exchange inside and outside the bubble is estimated to be [52]: ΔE = − P(t)ΔV(t) + 4πR2 Δt eH2 O + 4πR2 Δtλ − πR3 Δt
MH2 O Lth 3
( ) ∑
n
Tliq − T
Q̇ = 4π R2 λmix (7) × ΔHi ri
Lth i=1
{ √̅̅̅̅̅̅ } (16)
R Rχ
Lth = min , (8) where ΔHi and ri are the enthalpy change and the rate of the ith re
π Ṙ
action, respectively, and eH2O is the energy transported by 1 mol of an
λmix, χ and Lth are the heat conductivity, thermal diffusivity of the gas evaporating or condensing water vapor, which is expressed by:
mixture and the thickness of the thermal boundary layer respectively.
3
Table 1
Scheme of the possible chemical reactions inside a collapsing argon bubble [79,97]. M is the third body. Subscript “f” denotes the forward reaction and “r” denotes the
reverse reaction. A is in (m3 mol− 1 s− 1) for two body reaction [(m6/mol2 s) for a three body reaction], and Ea is in (kJ/mol) and ΔH in (kJ/mol).
no Reaction Af nf Eaf Ar nr Ear ΔH
1 H2O + M ⇌ H●+●OH + M 1.912 × 107 − 1.83 28.35 2.2 × 1010 − 2.0 0.0 508.82
2 O2 + M ⇌ O + O + M 4.515 × 1011 − 0.64 28.44 6.165 × 103 − 0.5 0.0 505.4
3 ●
OH + M ⇌ O + H●+M 9.88 × 1011 − 0.74 24.43 4.714 × 106 − 1.0 0.0 436.23
4 H•+O2 ⇌ O+●OH 1.915 × 108 0.0 3.93 5.481 × 105 0.39 − 7.01 × 10-2 69.17
5 H●+O2 + M ⇌ HO● 2 +M 1.475 0.6 0.0 3.09 × 106 0.53 11.7 − 204.80
6 O + H2O⇌●OH+●OH 2.97 2.02 3.21 1.465 × 10-1 2.11 − 6.94 × 10-1 72.59
7 HO2 +H ⇌H2 + O2
● ●
1.66 × 107 0.0 1.97 × 10-1 3.164 × 106 0.35 13.3 − 239.67
8 HO•2+H●⇌●OH+●OH 7.079 × 107 0.0 7.06 × 10-2 2.027 × 104 0.72 8.8 − 162.26
9 HO●2 +O⇌ OH + O2
●
3.25 × 107 0.0 0.0 3.252 × 106 0.33 12.75 − 231.85
10 HO●2 + OH ⇌ H2O + O2
●
2.89 × 107 0.0 − 1.19 × 10-1 5.861 × 107 0.24 16.53 − 304.44
11 H2 + M ⇌ H●+H●+M 4.577 × 1013 − 1.4 24.98 1.146 × 108 − 1.68 1.96 × 10-1 444.47
12 O + H2 ⇌ H●+●OH 3.82 × 106 0.0 1.9 2.667 × 10-2 2.65 1.17 8.23
13 ●
OH + H2 ⇌ H●+H2O 2.16 × 102 1.52 8.25 × 10-1 2.298 × 103 1.40 4.38 − 64.35
14 H2O2 + O2 ⇌ HO● 2 +HO2
●
4.634 × 1010 − 0.35 12.12 4.2 × 108 0.0 2.87 175.35
15 H2O2 + M⇌●OH+●OH + M 2.951 × 108 0.0 11.59 1.0 × 102 − 0.37 0.0 217.89
16 H2O2 + H●⇌H2O+●OH 2.410 × 107 0.0 9.5 × 10-1 1.269 × 102 1.31 17.08 − 290.93
17 H2O2 + H●⇌H2 + HO● 2 6.025 × 107 0.0 1.9 1.041 × 105 0.70 5.74 − 64.32
18 H2O2 + O⇌●OH + HO● 2 9.550 2.0 9.5 × 10-1 8.66 × 10-3 2.68 4.45 − 56.08
19 H2O2+ OH ⇌ H2O + HO●
●
2 1.0 × 106 0.0 0.0 1.838 × 104 0.59 7.4 − 128.67
20 O3 + M ⇌ O2 + O + M 1.6x107 0 0 – – – − 96.20
21 O3 + O ⇌ O2 + O2 5.2x106 0 2090 – – – − 396.14
22 O3+●OH ⇌ O2 + HO● 2 7.8x105 0 960 – – – − 164.95
23 O3 + HO● 2 ⇌O2 + O2+ OH
●
1X105 0 1410 – – – − 121.92
24 H●+ O3 ⇌ HO● 2 +O 9x106 0.5 2010 – – – 135.65
25 H●+ O3⇌●OH + O2 1.6x107 0 0 – – – − 96.20
Third body efficiency factors: R1: αH2 = 0.73, αH2O = 12, αAr = 0.38; R2: αH2 = 2.5, αH2O = 12, αAr = 0.75; R3: αH2 = 2.5, αH2O = 12, αAr = 0.83; R5: αH2 = 1.3, αH2O =
14, αAr = 0.67; R11: αH2 = 2.5, αH2O = 12; R15: αH2 = 2.5, αH2O = 12, αAr = 0.64; R20: αO2 (forward) = 1.64, αO2 (backward) = 1.63, αH2O(backward) = 15.
Table 2
Scheme of the possible chemical reactions inside a collapsing CCl4-Ar bubble [63,79,98,99]. M is the third body. Subscript “f” denotes the forward reaction and “r”
denotes the reverse reaction. A is in (m3/mol s) for two body reaction [(m6/mol2 s) for a three body reaction], and Ea is in (kJ/mol) and ΔH in (kJ/mol).
Reaction Af nf Eaf Ar nr Ear ΔH
1 H2O + M ⇌ H●+●OH + M 1.912 × 107 − 1.83 28.35 2.2 × 1010 − 2.0 0.0 508.82
2 O2 + M ⇌ O + O + M 4.515 × 1011 − 0.64 28.44 6.165 × 103 − 0.5 0.0 505.4
3 ●
OH + M ⇌ O + H●+M 9.88 × 1011 − 0.74 24.43 4.714 × 106 − 1.0 0.0 436.23
4 H●+O2 ⇌ O+●OH 1.915 × 108 0.0 3.93 5.481 × 105 0.39 − 7.01 × 10-2 69.17
5 H●+O2 + M ⇌ HO● 2 +M 1.475 0.6 0.0 3.09 × 106 0.53 11.7 − 204.80
6 O + H2O ⇌ ●OH+●OH 2.97 2.02 3.21 1.465 × 10-1 2.11 − 6.94 × 10-1 72.59
7 HO2 +H ⇌H2 + O2
● ●
1.66 × 107 0.0 1.97 × 10-1 3.164 × 106 0.35 13.3 − 239.67
8 HO●2 +H ⇌ OH+ OH
● ● ●
7.079 × 107 0.0 7.06 × 10-2 2.027 × 104 0.72 8.8 − 162.26
9 H2 + M ⇌ H●+H●+M 4.577 × 1013 − 1.4 24.98 1.146 × 108 − 1.68 1.96 × 10-1 444.47
10 O + H2 ⇌ H●+●OH 3.82 × 106 0.0 1.9 2.667 × 10-2 2.65 1.17 8.23
11 ●
OH + H2 ⇌ H●+H2O 2.16 × 102 1.52 8.25 × 10-1 2.298 × 103 1.40 4.38 − 64.35
12 H2O2 + M⇌●OH+●OH + M 2.951 × 108 0.0 11.59 1.0 × 102 − 0.37 0.0 217.89
13 H2O2 + O ⇌ ●OH + HO● 2 9.550 2.0 9.5 × 10-1 8.66 × 10-3 2.68 4.45 − 56.08
14 O3 + M ⇌ O2 + O + M 1.6x107 0 0 – – – − 96.20
15 CCl4 ⇌ CCl3+ Cl
● ●
3.236 × 1022 − 2.29 288.9 3.388 × 1010 − 1.29 − 5.9 288.245
16 ●
CCl3⇌ :CCl2+●Cl 1.09 × 109 0.0 228.1 1.0 × 104 0.0 0.0 281.874
17 2●CCl3 ⇌ C2Cl6 4.55 × 106 − 1.6 1.5 3.83 × 1026 − 4.5 288 − 304.4
18 2●Cl + M ⇌ Cl2 + M 1.0 0.23 − 45.9 3.981 × 107 0.0 198.5 − 242.604
19 C2Cl6+●CCl3 ⇌ CCl4 + C2Cl5 7.94 × 105 0 59.9 2.95 × 102 0.8 39.5 34.167
20 C2Cl5 + Cl2 ⇌ C2Cl6+●Cl 2.04 × 105 0.0 9.9 3.51 × 1011 − 1.1 64.7 − 79.81
21 C2Cl5+●Cl ⇌ C2Cl4 + Cl2 2.45 × 107 0.0 0.0 6.37 × 109 − 0.4 195 − 184.502
22 ●
Cl + H2 ⇌ HCl + H● 94.56 1.72 12.837 55.99 1.72 9.09 4.4
23 CCl4 + H●⇌HCl+●CCl3 172 1.8 17.14 1.67 × 10-7 3.72 155.36 − 143.4
24 ●
Cl + H2O⇌ ●OH + HCl 1.17 × 102 1.67 63.84 4.12 × 10-1 2.12 − 5.37 65.514
25 2C2Cl5 ⇌ C2Cl6 + C2Cl4 8.13 × 105 0.0 59.03 3.023 × 102 0.76 38.63 − 264.31
26 Cl2 + H2O ⇌ HOCl + HCl 64.56 0.72 10.8 43.1 1.03 8.7 73.775
eH2O = Cv,H2O T (17) taken into account, involving H2O, H●, O, ●OH, HO● 2 , H2O2, H2, O2,
CCl4, ●CCl3, :CCl2, ●Cl, Cl2, C2Cl4, C2Cl5, C2Cl6, HCl and HOCl chemical
In the absence of carbon tetrachloride, the chemical kinetic model in
species. The scheme of Table 2 includes 12 reversible reactions for Cl
Table 1 is composed of 25 chemical reactions and their backwards re
containing species, which are the principal reactions reported for CCl4
actions involving H2O, H●, O, O3, ●OH, HO● 2 , H2O2, H2 and O2 chemical
sonochemistry [8–10,19–22,24,28,59–62]. Additionally, the reaction
species. This scheme has been partially validated from hydrogen flame
scheme of Table 2 has been partially validated through the different
studies [57], shock-tube and reactor-type experiments [58] as well as
experimental works conducted in RF plasma reactor [63] and shock-
single bubble sonochemistry [11]. For a bubble initially containing
tube experiment [64], for CCl4 pyrolysis. For a theoretical point of
carbon tetrachloride in addition to argon and water vapor, a chemical
view, a significant number of reactions (and products) can effectively be
kinetic model consisting in 26 reversible chemical reactions (Table 2) is
4
suspected for the CCl4 pyrolysis. Also, the reaction scheme may be more reactions are assumed to have the following Arrhenius temperature
and more complicated depending on the operational conditions, like dependence [12]:
CCl4 concentration and the type and the composition of the saturation ( )
Eafi
gas. This has been confirmed through the different experimental works kfi = Afi T bfi exp − (21)
Rg T
conducted in RF plasma reactor [63] and shock-tube experiment [64].
However, in sonochemistry and inside the bubble (micro-reactor), the ( )
Eari
space available for chemical reactions is quite different (small and kri = Ari T bri exp − (22)
Rg T
varying volume), in addition, the time available for chemical reactions is
very short (µs). Moreover, other phenomena are expected such as heat where Rg is the universal gas constant, Afi (Ari) is the pre-exponential
exchange, variation of reactor volume, segregation of vapor and gas factor, bfi (bri) is the temperature exponent and Efi (Eri) is the activation
content of bubble, light emission, etc. Consequently, it is clearly energy. Arrhenius parameters of each chemical reaction are presented in
deduced that the acoustic cavitation is a different environment for Tables 1 and 2.
chemical reactions, therefore, depending on the initial composition of The water vapor change with time inside the bubble, due to the
the bubble, the kinetical mechanism is very limited. In our case, because evaporation and condensation at the bubble wall and due to chemical
argon is used as a saturating gas, the present work is based principally on reactions is given by [65]:
the experimental work of Hua and Hoffmann [10], where the principal
ṁ
products of CCl4 sono-pyrolysis under argon atmosphere are the reactive nH2 O (t + Δt) = nH2 O (t) + 4πR2 Δt + VΔtU̇ H2 O (23)
M H2 O
chlorine species, C2Cl4, C2Cl6 and HOCl. Thus, we have limited our se
lection on the 12th reactions containing Cl species (reactions 15-26 of For other species k (except Ar):
Table 2) which are the main reactions responsible for the formation of
the early indicated species [10]. nk (t + Δt) = nk (t) + VΔtU̇ k (24)
Rate expressions for the chemical reactions consider elementary In general, there are three types of acoustic bubbles: (i) dissolving
reversible reactions involving K chemical species, which can be bubbles, (ii) stable (degassing) bubbles, and (ii) transient bubbles. The
expressed in the general form as [12]: latter is the interesting ones for sonochemistry (i.e., active bubbles),
∑
K ∑
K because it gives us the violent collapse and generation of the different
(18) species. This type of bubbles expands and collapses violently (with
′
υki Xk ⇌ υ′′ki Xk
k=1 k=1 nonlinear manner) accumulating higher temperature and pressure
in which υki is the stoichiometric coefficient of the ith reaction and Xk therein (~1000 to 8000 K), thereby generating chemical oxidants with
is the chemical symbol for the kth species. The superscript ‘ indicates molar yield on oxidants superior or equal the threshold yield at the end
forward stoichiometric coefficients, while “ indicates reverse stoichio of the bubble collapse. Therefore, the conditions under which the bubble
collapses were determined by resolving the bubble dynamic equation
metric coefficients. The production rate U of the kth species can be
∙
k (Eq. (1)) under diverse conditions of frequency, acoustic intensity and

written as a summation of the rate of the variables for all reactions initial ambient bubble radius (R0). The methodology of how deter
involving the kth species [12]: mining the profiles (vs. time) of bubble temperature, pressure, wall ve
locity and chemical species inside the bubble are all illustrated in the
1 dnk ∑
I
following section. If under such conditions the achieved maximum
(19)
′
U̇ k = (υ′′ − υ )ri (k = 1, …, K)
V dt i=1 bubble temperature at the collapse is enough higher to generate oxidant
where nk is the number of moles of the kth species. The rate ri for the with molar yield ≥ the threshold yield, therefore, the transient collapse
th
i reaction is given as [12]: is happened, if it is not the case, the bubble is either dissolving or
degassing (no collapse is occurred).
∏
K ′ ∏
K
(20)
′′
ri = kfi [Xk ]υki − kri [Xk ]υki
k=1 k=1
2.2. Methodology of resolution
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, respec The modified Keller-Miksis equation (Eq. (1)), is a nonlinear second-
tively. In the presence of a third body (M), reaction rate expression (Eq. order differential equation, which can be reduced to a system of two
∑
(20)) should be multiplied by [ (αki)(Xk)], (k = 1,…K), where αki is the differential first-order equations as
third body effeciency factor of the kth species in the ith reaction. If it is dR
not mentioned in Table 1, αki = 1 for all species. However, due to the = Ṙ (25)
dt
unavailability of αki in literature for the chemical mechanism given in
{ ( )[ ( ( )) ] ( ) ( ) ( )}
1 Ṙ R m̈R Ṙ ṁ ṁ ṁ Ṙṁ R dPB 3 2 Ṙ 2ṁ
ρL 1+ PB (t) − PA sin 2πf t + C
C
− P∞ + ρ 1 − C
+ CρL
+ρ Ṙ + 2ρL
+ 2CρL
+ CρL dt
− 2
Ṙ 1− 3C
+ 3CρL
L L
ḋR
= ( )
dt
1− Ṙ
C
+ Cṁρ R
L
Table 2 (in presence of CCl4), αki is equal to 1 for all species (equal
contribution for all substances). The role of the third body is removing Eq. (15), (25) and (26) are solved using finite difference method
the excessive of energy (eventially dissipated as heat) and stabilize the (Fortran 95). The numerical simulations start from time t = 0 (µs) with
chemical products. The forward and reverse rate constants for the ith the initial conditions that: R = R0, dR/dt = 0, T = Tliq, dPB/dt = 0, dm/
5
dt = 0, d2m/dt2 = 0. The outputs of these equations are the variation of R0 (absent of ultrasound). The initial pressure of CCl4 within the bubble
bubble temperature, evolution of the bubble radius and the variation of is governed by Henry’s law: PCCl4,0 = KH,CCl4CCCl4,0 (KH,CCl4 = 6624 Pa
the bubble wall velocity all along the bubble oscillation. Bubble pressure m3 mol− 1 [66]), where CCCl4,0 is the CCl4 concentration in the aqueous
is calculated using Eq. (3). The variation in time of number of moles of phase (i.e. varied from 0 to 5.2 mM). The water vapor pressure (Pv,0) is
each species housed within the bubble is given by Eqs. (23) and (24). calculated through Antoine’s equation (2.33 kPa at 20◦ C [67]). The PAr,0
The amount of argon remains unchanged during the bubble oscillation is calculated as PAr,0 = P0-(Pv,0 + PCCl4,0). Initial mole fractions of CCl4,
(i.e. chemically inert). The initial pressures of Ar, CCl4 and H2O inside H2O and Ar were calculated as Pi,0/P0, where i = CCl4, H2O and Ar.
the bubble satisfy the equilibrium relation: P0 = P∞ +2σ /R0, where P0 is Accordingly, the initial bubble content changes with the CCl4 concen
the internal bubble pressure (Pv,0 + PCCl4,0 + PAr,0) at equilibrium, R = tration in the liquid due to the change in PCCl4,0. For a concentration of
Fig. 1. (a and b). Evolution of the reactions system (and temperature) inside the bubble as function of time at around the end of the bubble collapse for (a) argon
bubble (0 mM of CCl4 in solution) and (b) CCl4-argon bubble (5.2 mM of CCl4 in solution). Simulation conditions for (a and b): frequency = 300 kHz, acoustic
intensity = 1 W/cm2, liquid temperature: 20◦ C, static pressure: 1 atm, ambient bubble radius R0 = 3.1 um. Vertical axes are in logarithmic scale.
6
5.2 mM of CCl4 in the liquid (water) at 20◦ C, initial mole fractions of chlorobenzene in the range from 35 to 1000 KHz. This study gives a
CCl4, H2O and Ar were 0.09 (9%), 0.0156 (1.56%) and 0.894 (89.4%), maximal degradation rate (and the maximal chloride ions production)
respectively. at 300 kHz for the three chlorinated contaminants. In addition, ac
It should be noted here that only the case of a single bubble cavita cording to the different experimental works, it has been demonstrated
tion is taken into account, where the different interactions between that the optimum ultrasound frequency is around 300 kHz, with regard
bubbles in the sonicated liquid are ignored. This assumption has been to the rate of oxidants production [84–88]. Therefore, the initial
made due to the complicated nature of multibubble systems (clusters) analysis of the effect of CCl4 concentration on bubble kinetics has been
which makes the process modeling more and more complex. Many conducted at 300 kHz. Moreover, the carbon tetrachloride solubility in
leader research groups in sonochemistry have adopted the single bubble water is ~5.2 mM at 20◦ C [66]. Consequently, we consider that the
approach for understanding the overall observed sonochemical effects maximal concentration of CCl4 is equal to 5.2 mM. The concentration of
(sonoluminescence and sonochemistry) in aqueous solutions, with CCl4 will be then varied in the range of 0 to 5.2 mM in order to cover the
relation to influencing factors [12,37,47,51,52,68–80]. Additionally, all whole range of carbon tetrachloride concentrations used in experi
simulations were conducted for argon-saturated water containing ments [8,17,21,28,34,89–91].
different concentrations of carbon tetrachloride, so, the initial bubble In Fig. 1(a and b), the evolution of chemical reactions inside an argon
content is a mixture of water vapor, argon and carbon tetrachloride. The bubble (a) and an argon-CCl4 bubble (b) is shown for a bubble driven by
complete bubble-dynamics model includes the liquid compressibility an ultrasound frequency of 300 kHz and an acoustic intensity of 1 W/
and viscosity, heat transfer (i.e. thermal conduction through bubble cm2. The liquid temperature and the ambient pressure are 20◦ C and 1
wall), mass transfer (i.e. non-equilibrium and condensation evaporation atm, respectively. The ambient bubble radius is fixed at 3.1 µm, which is
of the liquid vapor across the bubble/liquid interface), reaction kinetics found to be a typical value for an active bubble under a frequency of 300
occurring inside the bubble (i.e. reactions heats are incorporated). It kHz (see next sections). This ambient bubble radius (3.1 µm) is in good
should be noted that the evaporation and condensation of CCl4 at the agreement with that found experimentally by Brotchie at al. [45] and
bubble interface is ignored in our work. This choice is reinforced by the Pflieger et al [92], where the mean ambient bubble radii are 3.2 and 3.9
lower solubility of CCl4 (5.2 mM at 20◦ C) and its higher volatility (91 µm, respectively, for a frequency of 355 kHz. The analysis of Fig. 1(a)
mmHg at 20◦ C), therefore, the majority of CCl4 molecules are found and (b) is provided at around the end of bubble collapse (~2.47–2.476
within the bubble at t = 0. Note that in the theoretical work of Yasui µs).
[81], the non-equilibrium evaporation and condensation of methanol In Fig. 1(a), it is shown that the increase of bubble temperature to
have been considered. In addition, the diffusion of methanol molecules 4700 K (i.e., the maximum bubble temperature, Tmax) promotes the
and its effect on the evaporation and condensation of water molecules thermal dissociation of water vapor and consequently the generation of
(reduction of the available area for evaporation and condensation of various oxidants such as ●OH, O, O3, HO● 2 and H2O2, where the pro
water) are taken into account. However, all these considerations are ductions of these species at the end of bubble collapse (at Tmax) are 5.75
owing to the physical properties of methanol, which is completely × 10-17, 1.59 × 10-17, 5.06 × 10-24, 3.78 × 10-20 and 8.39 × 10-21 mol,
miscible in water, compared to CCl4 which has a very low solubility in respectively. It is also observed in Fig. 1(a) that the formation of H2 (3.9
water (5.2 mM, at 20◦ C). Moreover, methanol has a vapor pressure of 99 × 10-17 mol) and H● (1.77 × 10-17 mol) is in competition with that of O
mmHg, which is in the same range of that of CCl4 (91 mmHg). Therefore, and ●OH radicals, which is in good line with the results found by Yasui
it was found that the ignorance of non-equilibrium evaporation and [93] and Merouani et al. [79] for an argon bubble. On the other hand,
condensation of CCl4 is a good approximation for the numerical simu compared to the case of an argon bubble (Fig. 1(a)), the presence of
lations conducted in our work. This approach (i.e. ignorance of non- carbon tetrachloride inside the bubble (Fig. 1(b)) with a concentration
equilibrium evaporation and condensation of volatile compound) is of 5.2 mM in solution, causes the production of nine additional species
adopted by several researchers for the same aforementioned reasons. For (●CCl3, :CCl2, ●Cl, Cl2, HCl, HOCl, C2Cl4, C2Cl5 and C2Cl6). Moreover,
example, Authier et al. [82], Gireesan et al. [83] and Merouani et al. [70] the maximum temperature of the bubble is reduced to 3177 K, due to the
have all ignored the evaporation and condensation of carbon dioxide existence of CCl4 within the bubble and its endothermal dissociation. It
(solubility in water: 3.92 mM at 20◦ C) for the same reasons as those of is clearly observed in Fig. 1(b) that the chemistry of bubble is radically
CCl4. Note that the water vapor evaporation and condensation at the modified; where the yielding of the main species formed previously
bubble wall takes place even through that of CCl4 is ignored (discussion (Fig. 1(a)) is increased with the exception of H● and H2 molecules. The
of this point is provided in section 1 of the supplementary material). oxidants formed in this case (CCl4-Ar bubble) are: ●CCl3, :CCl2, ●Cl, Cl2,
-16
HOCl, ●OH, O, O3, HO● 2 and H2O2, with a yield of 5.42 × 10 , 2.38 ×
3. Results and discussions 10-17, 3.61 × 10-16, 1.44 × 10-17, 1.15 × 10-17, 9.9 × 10-17, 2.12 × 10-17,
For the control of the whole range of ambient bubble radii, a certain 2.1 × 10-22, 1.16 × 10-19 and 1.51 × 10-19 mol, respectively. The pro
amount of oxidants is fixed (very low value), which is the threshold of duction of H● and H2 goes down to 1.78 × 10-18 and 7.33 × 10-19 mol,
production (10-17 mol). We use this threshold because the active bubble respectively. Therefore, the total yield of reactive chlorine species (RCS:
population is controlled by their chemical yield not by their dynamical
●
CCl3, :CCl2, ●Cl, Cl2, HOCl) is 9.53 × 10-16 mol while that of reactive
parameters (i.e. bubble radius, bubble temperature/pressure, collapse oxygen species (ROS: ●OH, O, O3, HO● 2 and H2O2) is increased by 64%
time… [37,38]). Additionally, in the next sections, the ambient bubble compared to the case of argon bubble. The yielding improvement of ROS
radius (i.e., R0) denotes the bubble radius in the absence of ultrasound is owing to the reaction of CCl4 with hydrogen atoms (a good scavenger
irradiation, an active bubble denotes a bubble which is able to generate of H●, Reaction (23) of Table 2), which prevents the fast recombination
oxidants with yield ≥ the production threshold yield (10-17 mol), the reaction ●OH + H●+M ⇌ H2O + M (Reaction (1) of Table 2), thereby
range of active bubbles denotes the interval of R0 for bubbles achieving liberating higher concentration of ●OH and other ROS. This is confirmed
production yields of oxidants ≥ the production threshold yield (10-17 by the huge loss (~89%) in the yield of H● due to the presence of CCl4
mol) and the optimum ambient bubble radius (optimum R0) denotes the inside the bubble (i.e., 1.77 × 10-17 mol for Ar bubble compared to 1.78
ambient bubble radius at which the production rate of oxidant is × 10-18 mol for Ar-CCl4 bubble). Besides, the order of number of moles of
maximal. reactants at 2.47 µs is CCl4 > H2O, which is quite logic (for 5.2 mM of
CCl4), because if we consider the condensation of water vapor at the
bubble wall, the amount of H2O goes down even before its consumption
3.1. Effect of carbon tetrachloride on bubble kinetics through the different chemical reactions. This phenomenon is illustrated
Lim et al. [21] have investigated the effect of ultrasonic frequency on in Fig. S2 of the supplementary material , which gives the decrease of
the decomposition rate of carbon tetrachloride, chloroform and H2O (compared to CCl4 amount) with the condensation process in the
7
time interval 2–2.47 µs (the time interval just after 2.47 µs is illustrated production of new substances {i.e., reactive chlorine species (RCS):
in Fig. 1(b)). Thus, with regarding to the reactive species yield, CCl4 ●
CCl3, :CCl2, ●Cl, Cl2, HOCl}. The advantages of RCS is that can be
sonochemistry not only recompenses the loss in the bubble temperature formed at lower temperature than that required for ROS, as stated in
(loss in bubble energy) but also enhances the oxidants yielding and Fig. 1(a and b). Therefore, inactive bubbles of relatively lower temper
being the dominant factor which control the sono-activity of the bubble. atures (in the absence of CCl4) could be activated in the presence of CCl4
Fig. 1(a and b) also shows that the occurrence of chemical reactions thanks to the generation of RCS. Therefore, the shifting of the optimum
(Tables 1 or 2) inside the bubble at around the end of the bubble collapse ambient bubble radius (and the range of R0 for active bubbles) for the
is always accompanied by high bubble temperatures and pressures (i.e. maximal production of oxidants is more probable, especially due to the
4700 K and 2645 atm for argon bubble and 3177 K and 3138 atm for lower polytropic index of CCl4 (γCCl4 = 1.1, γAr = 1.67 and γH2O = 1.3)
argon-CCl4 bubble), this in spite of the endothermal character of the and its endothermal dissociation. This is confirmed according to Fig. 2
chemical reactions [65], which means that all reactions occurring within (a–d), which analyze the effect of CCl4 concentration in the liquid phase
the bubble use only a part of the bubble energy accumulated at the (5.2 mM) on the active bubbles-size variation for the production rate of
collapse. The other parts could be then released as mechanical energy reactive oxygen and chlorine species. For an argon bubble ([CCl4] = 0
(due to PV-work), heat and also light [94]. This issue has been well mM), all bubbles having an R0 in the range of 1–5 µm are chemically
confirmed in our recent published paper [65], in which the effect active for ROS production, whereas the dominant active bubbles are
(contribution) of each term of the bubble energy balance (i.e. chemical those of R0 ~3.1 µm (the optimum ambient bubble radius) (Fig. 2(a)).
reactions, heat exchange and mass transport) on the maximum bubble However, for the second case (CCl4-Argon bubble, Fig. 2(c)), this opti
temperature and pressure achieved at the collapse is shown. Our nu mum goes up to 6 µm for the maximal production of all the oxidants
merical analysis of Ref. [65] showed that chemical reactions did not play (ROS + RCS). For this last system, the range of R0 for active bubbles, i.e.
the dominant role in the bubble energy balance; conclusion retrieved ~1–11 µm, is more extended than the first case (Argon bubble, Fig. 2
over a wide range of simulations conditions (frequency and acoustic (a)). It should be noted that for the homogeneity of plots in Fig. 2(a and
intensity). Note that the sonoluminescence contribution in the bubble c), the threshold limit of oxidants production is fixed at 10-17 mol,
energy balance was not considered in our model. conversely to the previous cases [37,38], where this limit is reduced to
Different changes are produced by the evaporation of CCl4 into the 10-22 mol. The introduction of this modification is due to the fact that the
bubble such as the decrease of collapse temperature, increase of the decomposition of CCl4 inside the bubble increases largely its yielding as
molar yield of all species with the exception of H● and H2 and the well as the threshold limit of production. The reported production rates
Fig. 2. Variation, with respect to the ambient bubble radius, of (a) the normalized production rate of ROS (●OH, O, O3, HO2• and H2O2) for an argon bubble, (b) the
trapped water vapor amount and the maximum bubble temperature at collapse for an argon bubble (0 mM of CCl4 in solution), (c) the normalized production rate of
the sum of ROS + RCS (RCS: ●CCl3, :CCl2, ●Cl, Cl2, HOCl) for CCl4-argon bubble (5.2 mM of CCl4 in solution) and (d) the normalized trapped water vapor and CCl4
amounts and the maximum bubble temperature at collapse for the case of a CCl4-argon bubble (5.2 mM of CCl4 in solution). Simulation conditions for (a–d): fre
quency = 300 kHz, acoustic intensity = 1 W/cm2, liquid temperature: 20◦ C, static pressure: 1 atm. Curves of the trapped water vapor and CCl4 amounts as function of
R0 in absolute scale are given in Fig. S2 of the supplementary material.
8
in Fig. 2(a and c) have been normalized with respect to the maximal subsequently the large increase of molar heat of the bubble content. The
yielding (i.e., corresponding to R0,opt) obtained for each case (argon- same behavior explained in this section is observed in Refs. [37,38]. It
bubble and CCl4-argon bubble). should be noted that the optimum ambient bubble radius obtained in
From Fig. 2(a and c), it is seen that the optimum ambient bubble our study (3.1 µm, frequency = 300 kHz) is in good agreement with the
radius for the maximal production of oxidants {for argon-bubble (Fig. 2 experimental mean values of 3.2 and 3.9 µm, which have been reported
(a)) or CCl4-argon bubble (Fig. 2(c))} is shifted towards greater values by Brotchie at al. [45] and Pflieger et al. [92], respectively, for a fre
compared to the optimum R0 giving the maximal bubble temperatures quency of 355 kHz. The same explanation is applied for the case of CCl4-
{2 µm for argon-bubble (Fig. 2(b)) and 1.8 µm for CCl4-argon bubble argon bubble (Fig. 2(c and d)), where the optimum ambient bubble
(Fig. 2(d)}. This is explained by the competition between the maximal radius for the maximal production of ROS + RCS shifts to 6 µm. How
bubble temperature reached at collapse and the amount of vapor (and ever, in this case, the decrease of the bubble temperature (above 1.8
carbon tetrachloride for the case of CCl4-argon bubble) trapped inside µm, Fig. 2(d)) is ascribed to the increase of heat capacity of the bubble
the bubble. Note that curves of the amounts of water vapor and CCl4 due to the increase of both CCl4 and vapor amounts inside the bubble at
trapped at the collapse, reported in Fig. 2(b and d)), are normalized collapse (Fig. 2(d)). Moreover, the endothermal decomposition of CCl4
with respect to the maximum amounts obtained at the upper limit of R0 and vapor molecules participates in addition to the decrease of bubble
(11 µm). For example, for the case of argon-bubble, we observe that the temperature. As it can be seen in Fig. 2(d), from R0 = 6 µm (optimum
maximal bubble temperature as well as the amount of water vapor radius, Fig. 2(c)), the quantities of water vapor and CCl4 at collapse
gradually increased from R0 = 0.8 to 2 µm (Fig. 2(b)). Similarly, in increase rapidly. Consequently, the generation of oxidants (ROS and
Fig. 2(a), the production of ROS is improved until the bubble radius of RCS) goes down (Fig. 2(c)) proportionally with the drastic decrease of
2 µm, above this point, the bubble temperature starts to be decreased as bubble temperature (Fig. 2(d)). Nevertheless, the yield of ROS + RCS is
the vapor amount continues to go up. This is due to the increase of heat observed to be increased in the range of R0 between 1.8 and 6 µm (Fig. 2
capacity of gas/vapor mixture inside the bubble. On the other hand, the (c)), because in this range (1.8 to 6 µm), bubble temperature is rela
formation of ROS increases up to a bubble radius of 3.1 µm (Fig. 2(a)), tively large (Fig. 2(d)) to ensure the decomposition of CCl4 and water
because in the range of R0 = 2 to 3.1 µm, the bubble temperature is vapor as well as the generation of the different oxidants. In addition,
sufficiently large (Fig. 2(b)) to ensure the decomposition of water vapor from Fig. 2(a and c), it is seen that the range of R0 for active bubbles
molecules as well as the formation of the different oxidants. Above the under CCl4-argon system is clearly larger than that of argon-system
bubble radius of 3.1 µm (Fig. 2(a)), the oxidants generation (ROS) sole. This is explained by the thermal decomposition of CCl4 inside
slowly goes down with the decrease of the bubble temperature (Fig. 2 the bubble, where the amount of all species (ROS + RCS, with the
(b)). This is explained by the endothermic decomposition of vapor and exception of H● and H2) is increased in spite of the decrease of bubble
Fig. 3. (a–c). Evolution of the normalized production rates of ROS (a), RCS (b) and ROS + RCS (c) created inside the bubble at the collapse as functions of the
ambient bubble radius (R0) and CCl4 concentration in the solution (from 0 to 5.2 mM). ROS: reactive oxygen species (●OH, O, O3, HO● 2 and H2O2), RCS: reactive
chlorine substances (●CCl3, :CCl2, ●Cl, Cl2, HOCl). Simulation conditions for (a–c): frequency = 300 kHz, acoustic intensity = 1 W/cm2, liquid temperature: 20◦ C,
static pressure: 1 atm.
9
Table 3 Table 4
The size of active bubbles (range and optimum ambient radius) for the maximal Effect of acoustic intensity on the size of active bubbles (range and optimum
production of ROS (●OH, O, O3, HO2• and H2O2), RCS (●CCl3, :CCl2, ●Cl, Cl2, ambient radius) for the maximal production of all oxidants (ROS + RCS) as
HOCl,) and ROS + RCS as function of CCl4 concentration (0 to 5.2 mM). function of carbon tetrachloride concentration (0 to 5.2 mM). Simulation con
Simulation conditions: frequency = 300 kHz, static pressure = 1 atm and liquid ditions: frequency = 300 kHz, static pressure = 1 atm and liquid temperature:
temperature: 20◦ C. 20◦ C. ROS (●OH, O, O3, HO2• and H2O2) and RCS (●CCl3, :CCl2, ●Cl, Cl2, HOCl).
[CCl4], Range of ambient bubble radius (µm) Optimum bubble radius [CCl4], mM Range of ambient bubble radius (µm) Optimum bubble radius (µm)
mM (µm)
0.7 W/cm2 1 W/cm2 0.7 W/cm2 1 W/cm2
ROS RCS ROS + ROS RCS ROS +
0 2.3 – 3.4 1.5 4.8 ‫ــ‬ 2.7 3.1
RCS RCS
0.01 2.3 – 5.7 1.5 8.2 ‫ــ‬ 2.7 3.1
0 1.5 – 4.8 / 1.5 – 4.8 3.1 / 3.1 0.1 2.3 – 6.8 1.5 9.5 ‫ــ‬ 4.8 7.0
0.01 1.5 – 5.2 5.5 – 8.2 1.5 – 8.2 3.1 7.1 3.1 1 2.0 – 8 1.1 10.4 ‫ــ‬ 4.7 6.5
0.02 1.5–6 4.5 – 8.7 1.5 – 8.7 3.2 7.1 3.2 5.2 1.85 – 8.5 1.0 10.75 ‫ــ‬ 4.7 6.0
0.04 1.5–7 3.6 – 9.1 1.5 – 9.1 3.1 7.1 6.9
0.06 1.5–7.3 3.1 – 9.3 1.5 – 9.3 3.2 7.1 6.9
0.08 1.5 – 7.5 2.8 – 9.4 1.5 – 9.4 3.2 7.1 7.0 the large increase of oxidants yielding by the decomposition of CCl4
0.1 1.5 – 7.5 2,7 – 9.5 1.5 – 9.5 3.3 7.1 7.0
within the bubble.
0.5 1.5 – 8.3 1.5 – 10.2 1.3 – 10.2 5.5 6.8 6.7
1 1.4 – 8.5 1.2 – 10.4 1.1 – 10.4 5.5 6.5 6.5
In Fig. 3(a), it is seen that the optimum bubble radius for the maximal
3 1.3 – 8.7 1.1 – 1.1 – 10.74 5.5 6.3 6.0 production rate of ROS is shifted from 3.1 µm towards ~5.5 µm pro
10.74 portionally with the increase of CCl4 concentration (observation valu
5.2 1.3 – 8.7 1.0 – 1.0 –10.75 5.3 6.1 6.0 able for [CCl4] ≥ 0.5 mM (see Table 3)). The transition of the optimum
10.75
bubble radius towards greater values is rapid for CCl4 concentrations
greater than 0.1 mM. The explanation of the observed behavior in Fig. 3
temperature (Fig. 2(c and d)). Analyzation of these results indicates (a) is due to the fact that the maximal production of oxidants (for CCl4-
that it is very interesting to study the impact of CCl4 concentration (in argon bubble) is shifted towards higher ambient bubble radius (Fig. 3
solution) on the range of R0 for active bubbles as well as the optimum (b)) in spite of the decrease of bubble temperature (Fig. 2(d)). Conse
R0 for the maximal production of oxidants. quently, the maximal yielding of the RCS is moved to around 6–7 µm
(Fig. 3(b) and Table 3). Therefore, the maximal production of ROS is
shifted towards higher ambient bubble radii especially for CCl4 con
3.2. Effect of carbon tetrachloride on the range of active bubble sizes centrations greater than 0.1 mM. As a result, the optimum bubble radius
for the maximal production of all oxidants (ROS + RCS) is shifted to
In Fig. 3(a), the normalized variation of reactive oxygen species wards higher bubble radii, 6–7 µm, with the exception of CCl4 concen
production (ROS: ●OH, O, O3, HO● 2 and H2O2) is given for CCl4 con trations that are equal or lower than ~0.02 mM (Fig. 3(b) and Table 3).
centrations from 0 to 5.2 mM, where CCl4 concentration of 0 mM refers This is because for these CCl4 concentrations (≤0.02 mM), the yield of
to the argon bubble. In literature, all used concentrations of CCl4 are in the RCS is lower than that of ROS (data not shown). Consequently, the
this range of 0 to 5.2 mM [8,17,21,28,34,89–91]. In Fig. 3(b), the evo maximal response is found at around 3.1 µm (Fig. 3(c) and Table 3). In
lution (normalized yielding) of the reactive chlorine species (RCS: Table 3, the ranges of active bubbles in addition to the optimum bubble
●
CCl3, :CCl2, ●Cl, Cl2 and HOCl) is shown for CCl4 concentration from radii are given in details compared to Fig. 3(a–c). These results indicate
0.01 to 5.2 mM. Fig. 3(c) shows the normalized production rate of the that for CCl4 concentrations greater than ~0.02 mM, the optimum
total oxidants amount (ROS + RCS) for the same CCl4 concentration as bubble radius for the maximal production of ROS and RCS is shifted
in Fig. 3(a and b). Fig. 3(a–c) are plotted for a frequency of 300 kHz and rapidly towards the higher bubble radii ~6–7 µm, whereas, for CCl4
an acoustic intensity of 1 W/cm2, where the threshold limit of oxidants concentrations lower than this value (0.02 mM), this optimum is found
production is fixed at 10-17 mol as in the previous section (Fig. 2(a and at around ~3.1 µm.
c)). The normalized production rate (y-axes) in Fig. 3(a–c) is defined as
the production rate of ROS, RCS or ROS + RCS obtained for each R0 of
the investigated interval divided by the maximal production rate of the 3.3. Impact of acoustical parameters on the range of active bubbles in
same parameters, i.e. ROS, RCS or ROS + RCS, obtained at the corre presence of CCl4
sponding optimum R0. For the conditions of Fig. 3(a–c), optimum R0′ s
are regrouped in Table 3 as function of CCl4 concentration, for ROS, RCS Table 4 shows the calculated size distribution of active bubbles (and
and ROS + RCS. The use of normalized amounts is obligatory for this optimum radii) as function of CCl4 concentration in the bulk liquid. This
case (Fig. 3), for the homogeneity of the different curves, because of the table gives the maximal production of all oxidants (ROS + RCS). These
difference in production with respect to R0 (especially for the low con results are obtained for a frequency of 300 kHz, under the acoustic in
centrations of CCl4).The necessity of this choice is illustrated in Fig. S3(a tensities of 0.7 and 1 W/cm2. The threshold limit of the total oxidants
and b) of the supplementary material, in which data of Fig. 3(a and b) production is fixed at
are given in absolute values. As it can be seen from Fig. S3(a and b), the 10-17 mol as in the previous sections. This Table shows that the same
use of the absolute amounts of ROS and RCS, reduces our capacity of behavior is observed for both intensities, where the rise of CCl4 con
analyzing the range of active bubbles and the optimum R0, especially for centration in solution causes the range of active bubbles to be enlarged (i.
the low concentrations of CCl4. e., increase of overall production). However, the decrease of acoustic
For an argon bubble, it is obvious that no reactive chlorine species intensity (0.7 W/cm2) narrows the range of active bubbles for each CCl4
are produced (CCl4 is absent in solution). Fig. 3(a–c) show that the in concentration. This is explained by the fact that when the acoustic in
crease of CCl4 concentration in solution causes the range of active tensity is increased above the Blake threshold more bubbles are induced
bubbles (for oxidants yielding) to be enlarged. This is clearly due to the to produce violent collapses (increase of vapor amount, time of collapse
thermal decomposition of CCl4 inside the bubble, where new elements and bubble temperature) [37], which increases the range of sono
are created (e.g., RCS). In addition, the reaction of CCl4 with hydrogen chemically active bubbles. On the other hand, it is shown in Table 4 that
atom promotes more the formation rate of ●OH radicals as well as that of the maximal response (optimum bubble radius) is moved towards greater
O, O3, HO● 2 and H2O2 molecules. This enlargement is observed in spite of radii as the acoustic intensity goes up, where the cases of CCl4 concen
the decrease of bubble temperature (see Fig. 2(c and d)), which indicates tration greater than ~0.01 mM seem to be relatively more affected by this
10
Table 5 respectively) starts to be affected by the existence of carbon tetrachlo

Experimental and theoretical ambient bubble sizes for various carbon tetra ride inside the bubble when its concentration in the bulk liquid is at
chloride concentrations (0 to 5.2 mM) and ultrasound frequencies (355, 515, around 0.1 mM. For CCl4 concentrations greater than 0.1 mM, the op
875 and 1000 kHz). The optimum R0 (obtained in our work) give the maximal timum ambient bubble radius shifts toward higher values especially for
yielding of all oxidants (ROS + RCS) created inside the bubble at the strong the ultrasound frequencies 355 and 515 kHz (Table 5). This trend is due
collapse. Simulation conditions: acoustic intensity: 1 W/cm2, static pressure: 1
to the increase of CCl4 concentration in solution as well as its mole
atm and liquid temperature: 20◦ C. ROS (●OH, O, O3, HO2• and H2O2) and RCS
fraction inside the bubbles, which means that more bubbles are acti
(●CCl3, :CCl2, ●Cl, Cl2, HOCl).
vated by the increase of their molar yield (CCl4 and H2O thermal
Frequency 300 kHz 515 kHz 875 kHz 1000 kHz
dissociation). Therefore, the optimum radius is shifted toward higher
Mean R0 (experimental) 3.2 µm (air, 3.0 µm 2.7 µm 2.0 µm value through the phenomenon of competition between bubbles tem
355 kHz)a (air)a (air)a (air)a peratures and the amount of CCl4 and H2O within these acoustic cavities
3.9 µm (Ar,
(see section 3.1). However, the increase of CCl4 concentration greater
355 kHz)d
Optimum ambient bubble radius, R0,opt (µm) than 0.1 mM has a slight negative impact on the localization of the
Oxygen bubble 4.8b 3b 1.86b 1.6b optimum radius, where for example for 355 kHz and CCCl4 = 5.2 mM,
Argon bubble ([CCl4] = 3.1c 2.4c 1.9c 1.7c this optimum shifts to 6 µm. This behavior is explained by the negative
0 mM)
effect of CCl4, due to its lower polytropic index (1.11) and endothermal
[CCl4] = 0.01 mM 3.1c 2.4c 2.0c 1.9c
[CCl4] = 0.1 mM 7.0c 3.1c 2.0c 1.9c
dissociation.
[CCl4] = 1 mM 6.5c 3.1c 2.0c 1.8c
[CCl4] = 5.2 mM 6.0c 3.1c 1.9c 1.8c 4. Conclusion
a
Brotchie et al. [45] (mean R0).
b
Merouani et al. [39]. In this work, a theoretical investigation was conducted for the first
c
This study. time in order to reveal the impact of CCl4 concentration (in solution) on
d
Pflieger et al. [92]. the size distribution of active bubbles as well as the variation of opti
mum R0 for the maximal production of oxidants (ROS and RCS). The
increase of intensity. This is owing to the fact that when the acoustic numerical simulations of chemical reactions inside the bubble (in
intensity is increased for CCl4 concentrations greater than 0.01 mM, more presence of CCl4) indicate that for CCl4 concentrations greater than 0.02
species are generated from the thermal dissociation of CCl4 and water mM (frequency = 300 kHz), the optimum bubble radius for the maximal
vapor. Consequently, the enhancing impact of CCl4 toward ROS and RCS yielding of ROS and RCS is shifted rapidly towards higher bubble radii
is more pronounced for the case of 1 W/cm2 compared to that of 0.7 W/ ~6–7 µm. Whereas, for CCl4 concentrations lower than 0.02 mM, this
cm2. The higher optimum bubble radii obtained at 1 W/cm2 are logically optimum is found at around ~3.1 µm (the same as that retrieved for an
explained by the enlargement of the active bubbles range; because more argon-bubble). It has been found that the range of active bubbles and the
this range is wider, the maximal response is shifted towards greater optimum size increased with the rise of acoustic intensity, where this
ambient bubble radii. Conversely, the decrease of acoustic intensity re impact is more pronounced for CCl4 concentrations greater than 0.01
duces more the range of active bubbles as well as the value of optimum mM. A good agreement is found between our results and those obtained
radius. These results are in line with those found by Merouani et al. by experimental or theoretical works, where it has been shown that for
[38,47], either for the maximal production of hydrogen or the oxidizing higher frequencies (875 and 1000 kHz), the presence of CCl4 in solution
species. In addition, this trend is observed for other experimental and (for all concentrations) has no effect on the optimum bubble radius.
theoretical works either for sonoluminescing [37,45,95] or sonochemi However, at 300 and 515 kHz, this optimum starts to be increased when
cally [38,96] active bubbles. Labouret and Frohly [40] demonstrated CCl4 concentrations is at around 0.1 mM.
experimentally at 350 kHz and 1.1 MHz that the increase of acoustic Finally, it should be noticed that the bubble size distribution may
intensity causes the size distribution of active bubbles to be wider and the also be affected by the presence of volatile compounds other than CCl4 in
optimum R0 to be larger. the aqueous liquid. However, the suspected effect depends on many
On the other hand, the effect of ultrasound frequency on the opti factors such as the reactivity of this element with ROS and its ability to
mum R0 for the maximal production of ROS and RCS is revealed in generate other oxidants through pyrolysis. If the organic element is
Tabale 5 for the range of 300–1000 kHz. The citation of the range of nonvolatile and hydrophilic, this means that our element will be present
active bubbles at each frequency was omitted due to the great disparity in the bulk liquid during the bubble oscillation, which means that
observed between the total oxidants production (in presence of CCl4) for probably this organic compound will have no impact on bubbles dis
high and low frequencies. For example at 1000 kHz (In = 1 W/cm2) and tribution especially when its concentration in solution is low. Besides, it
in presence of CCl4 inside the bubble, the maximal production of oxi should be noted that the direct control of the ambient bubble sizes is
dants is around 10-22 mol. In contrast, at 300 kHz (in presence of CCl4), impossible, however, through ajusting the different operational pa
the maximal production of all oxidants ranges from 10-17 to 10-15 mol. rameters (frequency, intensity, dissolved gas, liquid temperature and
This trend indicates the narrowness of the size distribution of active compositions…), we can affect and direct the tendency to improve the
bubbles as the ultrasound frequency is increased, which is in total population of ambient bubble radii. This issue has been demonstrated
accordance with the experimental determinations [45]. experiemntally and theorticaaly in many research studies (e.g. see Refs.
In Table 5, the experimental results (mean R0) of Brotchie et al. [45] [37,38,41–47]).
(for air bubbles, without CCl4) and Pflieger et al. (Ar-flow, without CCl4)
[92], the theoretical findings of Merouani et al. [39] (for oxygen bubbles, Declaration of Competing Interest
without CCl4) and our simulations results (argon bubbles) are collected,
for various frequencies of ultrasound. As it can be seen, the optimum The authors declare that they have no known competing financial
R0′ s obtained for an argon bubble (0 mM of CCl4) are consistent with the interests or personal relationships that could have appeared to influence
mean R0′ s found experimentally by Brotchie et al. [45] and Pflieger et al. the work reported in this paper.
[92], even through a direct comparison cannot be made due the dif
ference in the studied systems (single bubble for our case and water, i.e. Acknowledgements
multibubble system, for the experimental works). At 300 and 515 kHz, it
seems that the optimum ambient bubble radius (3.1 and 2.4 µm, This study was supported by The Ministry of Higher Education and
Scientific Research of Algeria (project No. A16N01UN250320180001)
11
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