11636 J. Phys. Chem.

1996, 100, 11636-11642

Kinetic Model for the Sonochemical Degradation of Monocyclic Aromatic Compounds in

Aqueous Solution

Alex De Visscher,* Peter Van Eenoo, David Drijvers, and Herman Van Langenhove
Department of Organic Chemistry, Faculty of Agricultural & Applied Biological Sciences, UniVersity of Ghent,
Coupure Links 653, B-9000 Gent, Belgium
ReceiVed: December 13, 1995; In Final Form: April 3, 1996X

The breakdown of benzene, ethylbenzene, styrene, and o-chlorotoluene in aqueous solution by 520 kHz
ultrasonic waves was studied at various initial concentrations in the millimolar range. First-order reaction
rates depend upon both initial concentration and sonication time. These variations can be explained by a
model that combines some physical and chemical aspects of sonochemistry. The basic assumptions of the
model are first-order pyrolysis in the cavitations yielding both reactive/volatile and inert/nonvolatile products,
and lowering of the maximum cavitation temperature due to the presence of the organic compounds in the
bubble phase. Despite the necessary assumptions and approximations in order to limit the number of adjustable
parameters, the lack of fit standard deviation after regression was as low as 4-9.2%.

Introduction The production of OH radicals in an ultrasonic field can be

It is well established that the violent collapse of cavitation
bubbles in an ultrasonic field causes extremely high local
temperatures, although estimated values vary widely.1-6 How-
ever, the present knowledge about the mechanism of sonochem-
ical breakdown of organic compounds is limited. Two reaction
mechanisms have mainly been proposed to explain the chemical
and kinetic data.
The first mechanism is pyrolysis in the cavitation bubbles.
The second mechanism is the generation of OH radicals in the
cavitation bubbles, which subsequently oxidize the organic
compounds.
Pyrolysis is expected to be the main reaction path for the
degradation of apolar compounds. Lamy et al.7 found that the
sonication of benzene and chlorobenzene yields acetylene and
no hydroxylated compounds.
Kinetic data of the sonochemical degradation of apolar
compounds is scarce. Bhatnagar and Cheung8 studied the
destruction of some chlorinated hydrocarbons by 20 kHz
ultrasonic waves and fitted first-order kinetics to their data. The
influence of the initial concentration was not reported to be
checked. The reaction rates of degradation were found not to
depend upon the presence of other reacting compounds, but the
scatter of the kinetic data is up to 35%, too large to rely on this
conclusion.
Cheung and Kurup9 studied the sonochemical degradation
of two CFC’s in aqueous solution and found that the reaction
rate decreased during the course of the experiment. The pH
decrease during the course of the experiment was assumed to
cause this phenomenon. The effect was modeled kinetically
by introducing a “baseline concentration" of CFC that is not
degraded by the ultrasonic waves.
Hart et al.6 investigated the sonolysis of methane and ethane
in aqueous solution by 300 kHz ultrasound and found a
considerable decrease of the reaction rate at high concentrations.
Most hydrocarbons ranging from C1 to C4 could be found as
reaction products. By comparing the yield of ethane to the sum
of the yields of ethylene and acetylene, it was shown that the
temperature of cavitation decreased with increasing methane
concentration.
X Abstract published in AdVance ACS Abstracts, June 1, 1996.
S0022-3654(95)03688-4 CCC: $12.00
detected by ESR.10 OH radicals are not expected to influence
the breakdown of apolar compounds considerably, as CCl4 is
efficiently broken down by ultrasonic waves,8 although the
breakdown of CCl4 by OH radicals is negligible, compared to
other chlorinated hydrocarbons.11
Polar compounds exposed to ultrasonic waves are expected
to break down by OH radicals.7 Pétrier et al.12 investigated
the sonolysis of phenol in aqueous solution and found hydro-
quinone, catechol, and benzoquinone as reaction products.
These reaction products are attributed to the attack of the
hydroxyl radical on phenol. Further evidence is found in the
fact that the degradation rate of phenol is closely related to the
production rate of hydrogen peroxide. The zero-order degrada-
tion rate of phenol increases with increasing initial concentration
and reaches a plateau at concentrations between 5 and 10 mM.
The production rate of H2O2 decreases with increasing initial
phenol concentration, reaching a plateau in the same concentra-
tion range. The recombination of OH radicals, yielding H2O2,
appears to compete with the oxidation reactions.
Still, pyrolysis also occurs when polar compounds are
sonicated. Currell et al.13 found that the sonication of phenol
yields acetylene as well. The formation could be inhibited
almost completely by increasing the pH, thus ionizing the phenol
molecule. Increasing the pH also decreased the degradation of
phenol significantly, which shows that phenol degrades at least
partially by pyrolysis in the bubble phase.
Kotronarou et al.14 studied the sonolytical degradation of
p-nitrophenol in aqueous solution and interpreted the results
using an elaborate model involving both hydroxyl attack and
pyrolysis reactions. The model was incorporated in a reaction
scheme for the sonolytical degradation of parathion, a compound
that yields p-nitrophenol as reaction product.15
Hua et al.5 studied the hydrolysis of p-nitrophenol and
p-nitrophenyl acetate in the presence of ultrasound, with various
cavitating gases. The reaction rate appeared to depend on the
cavitating gas considerably. In both cases the reaction rates
were lowest in the case of He and highest in the case of Kr.
The use of Ar as cavitating gas yielded rates in between.
Murali Krishna et al.16 demonstrated that the composition of
alcohol-water mixtures influences the amount of pyrolysis in
the cavitation bubbles. This is due to a change in the
© 1996 American Chemical Society
Sonochemical Breakdown of Aromatic Compounds
Figure 1. Concentration vs time profiles of benzene in a semiloga-
rithmic diagram.
physicochemical properties of the solution. Fitzgerald et al.17
established that the nature of the gas dissolved into the liquid
influences the rate of the sonolysis reactions. Griffing18 noted
that volatile compounds such as diethyl ether lower the sonolysis
reactions due to a decrease of the specific heat ratio in the
cavitation phase. Gutiérrez and Henglein19 assumed that
alcohols inhibit the sonolysis of tetranitromethane the same way.
No attempt has so far been made to incorporate these changes
into a kinetic model of sonochemical degradation reactions.
Materials and Methods
Sonication experiments were performed with an Undatim
Ortho Reactor, producing 520 ( 1 kHz ultrasonic waves. The
high-frequency generator was equipped with an extra volt meter
to allow more accurate power calibration. Power was controlled
manually. Power transferred to the liquid (150 mL) was 14.6
W, measured calorimetrically. The reactor was a 200 mL glass
vessel with a cooling jacket. The cooling water was kept
constant at 25 °C, using a water bath with thermostat. Due to
the transferred power, the steady state reaction temperature was
29 ( 1 °C. The reactor was sealed with a screw cap. A syringe
needle was pierced through the septum of the screw cap for
sampling.
Samples (2 mL) were taken at various time intervals during
sonication, with a glass syringe. These samples were transferred
to small bottles and sealed with Mininert stoppers. A 1 vol %
2-hexanone solution (50 µL) was added as an internal standard.
A 1 µL sample of the mixture was analyzed by a Varian 3700
GC, equipped with an FID. A 15 m DB-5 capillary column of
0.53 mm i.d. with a 1.5 µm stationary phase was used for
separation. Helium was used as carrier gas, with a flow rate of
3.7 mL/min.
Benzene was purchased from Merck, and 2-hexanone, from
Janssen Chimica. All other chemicals were purchased from
Fluka. Purity of all chemicals was 99+%.
Experimental Results
Benzene was sonicated at initial concentrations of 3.38, 1.69,
0.9, and 0.45 mM. Figure 1 shows the concentration vs
irradiation time profiles of these experiments in a semiloga-
rithmic plot. For first-order reactions, this representation yields
straight lines. As can be seen from Figure 1, simple first-order
kinetics are not applicable to the sonolysis of benzene. The
first-order reaction rate appears to depend upon both concentra-
tion and sonication time. The experiments with initial concen-
trations 3.38 and 0.45 mM allow linear regression with good
fit. The first-order reaction rates are 0.001 71 ( 0.000 09 min-1
(n ) 13) and 0.023 08 ( 0.000 96 min-1 (n ) 8), respectively.
r exceeds 0.99 in both cases. The increase of the first-order
degradation rate is more than 13-fold, although pyrolysis
reactions are expected to be first order.
J. Phys. Chem., Vol. 100, No. 28, 1996 11637
Figure 2. Concentration vs time profiles of ethylbenzene in a
semilogarithmic diagram.
Figure 3. Concentration vs time profiles of o-chlorotoluene in a
semilogarithmic diagram.
TABLE 1: First-Order Reaction Rate Coefficients of the
Sonochemical Degradation of Ethylbenzene
initial sonication
concn time
(mM) (min) k (min-1) r
1 140 0.01667 ( 0.00191 0.993 (n ) 8)
0.5 100 0.03564 ( 0.00379 0.997 (n ) 6)
0.33 70 0.04333 ( 0.00243 0.998 (n ) 8)
The dimensionless Henry coefficient of benzene at 29 °C is
0.229.20 If it is assumed that headspace-water partitioning of
benzene after prolonged sonication is governed by Henry’s law,
a loss of 7% due to volatilization is expected. This would lead
to an overestimation of the degradation rate of 0.0012 min-1 in
a 1 h experiment. The overestimation is inversely proportional
to the sonication time. This means an overestimation of the
rates above of 11.7% and 2.2%, respectively.
Volatilization beyond the headspace is not expected, as the
solution becomes yellow upon sonication, even when the
reaction rate is extremely slow. A broad range of reaction
products is formed, including polar and nonpolar volatiles,
semivolatiles, and polymers. Work is currently being done to
identify these products.
Ethylbenzene sonolysis experiments were performed at initial
concentrations of 1, 0.5, and 0.33 mM. Higher concentrations
were not used because the solubility of ethylbenzene in water
is about 1.5 mM. The concentration vs time profiles are
presented in Figure 2, in a semilogarithmic plot. The deviation
from first-order kinetics is much less pronounced, but the
reaction rate depends on the initial concentration. Table 1 shows
the reaction rates. The increase is almost 3-fold upon decreasing
the initial concentration by a factor of 3. Although the
sonication time does not have a pronounced influence on the
reaction rate, the influence of the initial concentration is
comparable to the case of benzene.
Sonication of o-chlorotoluene was performed at initial
concentrations of 0.68, 0.34, and 0.17 mM. Figure 3 shows
the concentration vs time profiles in a semilogarithmic plot. The
profiles are very linear. The benzene experiment within this
concentration range yielded a linear plot as well.
11638 J. Phys. Chem., Vol. 100, No. 28, 1996 De Visscher et al.

concentration should be the same, irrespective of the initial

concentration. As can be seen from Figures 1-4, this is not
the case. Concentration profiles are always less steep when
the initial concentration is high. This can be explained by
considering the presence of reaction products that lower the
temperature rise upon cavitation as well. Therefore an adequate
model of sonochemical degradation should assume both reactant
and reaction products to influence the temperature upon
cavitation collapse.
If the number of cavitation bubbles is constant throughout
Figure 4. Concentration vs time profiles of styrene in a semilogarithmic
the experiment, the reaction rate observed is proportional to the
diagram.
reaction rate in the cavitations during collapse. Second, the
TABLE 2: First-Order Reaction Rate Coefficients of the concentration of the organics in the bulk liquid phase is assumed
Sonochemical Degradation of o-Chlorotoluene proportional to the concentration in the bubble phase. This
initial sonication could be due to Henry’s law, if diffusion of the compounds
concn time into the bubble is sufficiently rapid, or Fick’s law, if the transfer
(mM) (min) k (min-1) r is diffusion-controlled. As a result of these assumptions, the
0.68 105 0.02637 ( 0.00138 0.999 (n ) 8) reactions can be described with respect to the liquid phase, i.e.
0.34 75 0.02923 ( 0.00225 0.998 (n ) 6)
0.17 40 0.04145 ( 0.00223 0.999 (n ) 5) r ) kCl (1)
TABLE 3: First-Order Reaction Rate Coefficients of the with r the reaction rate related to the liquid phase (mM min-1),
Sonochemical Degradation of Styrene k the rate constant (min-1), and Cl the concentration of the
initial sonication compound in the liquid (mM). k obeys Arrhenius’ law:
concn time
(mM) (min) k (min-1) r k ) A exp(-E/RTc) (2)
0.97 80 0.01262 ( 0.00064 0.999 (n ) 9)
0.49 80 0.02409 ( 0.00233 0.995 (n ) 9) with A the Arrhenius proportionality factor (min-1), E the
0.25 40 0.03292 ( 0.00303 0.998 (n ) 5) activation energy (J/mol), R the universal gas constant (8.314
J/(mol K)), and Tc the temperature of the cavitation during
Table 2 shows the degradation rates for o-chlorotoluene. The collapse (K). Tc is attained by adiabatic compression:25
influence of the initial concentration is small, but this might be
due to the low concentrations used. Concentrations were kept Tc ) T(γ - 1)Pmax/Pmin (3)
low because exact solubility data of o-chlorotoluene was not
available. The solubility was estimated using the estimated with Pmax the maximum pressure in the liquid phase, Pmin the
value of the Henry coefficient of o-chlorotoluene21 and the vapor minimum pressure in the vapor phase, and T the minimum
pressure.22 The result was 1.5 mM. As the uncertainty upon temperature of the cavitation (K), assumed equal to the liquid
an estimated Henry coefficient is very large, a broad margin temperature. γ is the specific heat ratio cp/cv. This ratio
was taken. depends on the composition of the gas mixture in the cavitation.
Styrene was sonicated at initial concentrations of 0.97, 0.49, If the mole fraction of the organic compounds in the cavitation
and 0.25 mM. The concentration vs time profiles are shown is relatively small, then a linear relationship between the specific
in Figure 4 in a semilogarithmic plot. The first-order plots heat ratio of the mixture γ and the concentration Cl in the liquid
deviate slightly from linearity and are not parallel. Table 3 phase can be assumed.
shows the first-order reaction rates obtained in these experi-
ments. γ ) γ0 - KCl (4)

K is a proportionality constant (mM-1). This expression is

The Model
derived in Appendix A. The assumption of linearity will be
Pyrolysis reactions are expected to follow simple first-order discussed later on. Combining eqs 2-4 yields a relationship
kinetics. This means that parallel straight lines are expected in between the reaction rate constant and the liquid concentration:

( )
a semilogarithmic plot of the concentration vs time profiles.
This is clearly not the case. Reaction rates are higher at low E
k ) A exp - (5)
concentrations. Therefore, it can be assumed that the reaction RT(Pmax/Pmin)(γ0 - KC1 - 1)
conditions change as the concentration of the organic compound
decreases. As a cavitation bubble collapses, the gas inside is
compressed almost adiabatically. The temperature rise depends, The rate constant at infinite dilution is

( )
among other factors, upon the specific heat of the gas mixture. E
The vapor specific heat cp of aromatic compounds is of the order k0 ) A exp - (6)
of 120 J/(mol K),23 much higher than the specific heat of air
RT(Pmax/Pmin)(γ0 - 1)
(30 J/(mol K)) or water vapor (36 J/(mol K)).24 Therefore, the
adiabatic temperature rise upon compression of a cavitation is Combining eqs 5 and 6 yields
much lower if an aromatic vapor is present. Excessive amounts
of aromatic compounds lower the temperature of a collapsing
cavitation bubble, which lowers the rate of degradation.
If incorporation of the reactant concentration in the rate
k ) k0 exp -( EPminKC1
RTPmax(γ0 - 1)(γ0 - 1 - KC1) ) (7)

constant suffices to model the reaction kinetics, then the slopes

of the concentration profiles for a given compound at a given If KCl is small compared to γ - 1, then KCl is negligible in the
Sonochemical Breakdown of Aromatic Compounds
SCHEME 1: Assumed Reaction Scheme (S, reactant; P,
volatile products)
denominator. Thus it follows that
( )
EPminKC1
k ) k0 exp - (8)
RTPmax(γ0 - 1)2
This assumption will be discussed later on.
The only factor that is not a constant in the exponent is Cl.
Therefore, the equation can be written as follows:
k ) k0 exp(-aCl) (9)
Assuming that the concentration of the organic compounds is
sufficiently small leads to a very simple expression for the
reaction rate.
As mentioned before, the occurrence of reaction products has
to be accounted for. The reaction scheme assumed is shown
in Scheme 1. The reactant S is transformed to reactive products
P and inert products. In this context, a reaction product is
assumed reactive if it is volatile. Heavy products precipitating
in the liquid can be considered inert. Several assumptions are
made at this point.
First, the degradation rates of the reactant S and the reactive
products P into inert molecules are assumed equal. This reduces
the number of adjustable parameters by one, and it allows
consideration of the group S + P as one pseudospecies with
concentration Cl,2. This pseudospecies degrades with rate
constant k2 ) ka. The reactant degrades with reaction rate k1
) ka + kb.
Second, it is assumed that the concentration Cl in eq 4 can
simply be replaced by the concentration of the pseudospecies
Cl,2. This involves the assumption that the proportionality factor
between the concentration in the liquid phase and the concentra-
tion in the cavitations is the same for S and P. It also involves
the assumption that the specific heats of S and P are the same.
Third, it is assumed that the activation energies of all reactions
are the same. This allows the use of eq 9 with the same
parameter a for all reactions. In view of all these assumptions
and approximations, this model should be considered largely
empirical.
Eventually, the model consists of two reaction rates:
r1 ) k1,0 exp(-aCl,2)Cl,1 (10)
r2 ) fk1,0 exp(-aCl,2)Cl,2 (11)
r1 is the reaction rate of the reactant S, k1,0 is the rate constant
of the degradation of S at infinite dilution, and Cl,1 is the
concentration of S in the liquid phase. r2 and Cl,2 are the
reaction rate and the concentration of the pseudospecies S + P.
f is the fraction of S that is converted directly to inert reaction
products, and due to the aforementioned assumptions, f is also
the ratio between the rates of reactions 10 and 11.
Concentration vs time profiles are obtained by numerical
integration of the following differential equations:
dCl,1/dt ) r1 (12)
dCl,2/dt ) r2 (13)
J. Phys. Chem., Vol. 100, No. 28, 1996 11639
with a fourth-order Runge-Kutta routine.26 The time increment
was 0.5 min.
The model is fitted to a series of experimental concentration
profiles by nonlinear regression, using one set of adjustable
parameters. These parameters are k1,0, a, f, and the initial
concentration of every experiment. Regression was performed
on the logarithm of the concentrations, in order to obtain best
fit assuming constant relative uncertainty of the experimental
results. A Marquardt-Levenberg routine27 was used for regres-
sion.
Modeling Results and Discussion
The model results are represented in Figures 1-4 by the solid
lines. Agreement is obtained with no systematic error. The
parameters k1,0, a, and f are shown in Table 4, together with
the lack of fit standard deviation and the correlation coefficient.
All parameters are significantly different from zero, except
the values of f in the case of ethylbenzene and o-chlorotoluene.
This parameter influences the curvature of the concentration
vs time profiles. The insignificant values of f in the case of
ethylbenzene and o-chlorotoluene reflect the straightness of the
concentration profiles in a semilogarithmic plot. From a
mechanistic point of view, f equal to zero means that no
significant amount of inert products is formed. This is unlikely,
since the solution becomes turbid upon sonication. It is more
likely to assume that the reactive products formed have a
stronger influence on the temperature of the collapsing bubbles,
because of a larger partition coefficient between the liquid and
the bubble, a more rapid diffusion into the bubble phase, or a
higher specific heat, in conjunction with the stoichiometric factor
of the reaction product. More research is necessary to elucidate
this aspect of the mechanism. Therefore, no attempt has been
made to simplify the model in the case of ethylbenzene and
o-chlorotoluene by assuming that f equals zero. This would
provide too optimistic an estimation of the confidence intervals
of the parameters k1,0 and a.
All values of f differ significantly from 1, which indicates
that there are products that influence the cavitation indeed. Work
is currently being done to identify these products.
All values of a are significantly positive. This proves that
the presented model is superior to simple first-order kinetics.
The values of k1,0 and a do not vary substantially. k1,0 reflects
the reactivity of the compounds upon sonication. The partition
coefficient of the compound between the liquid phase and the
bubble phase will clearly influence k1,0. As mentioned before,
this partition coefficient can depend on the diffusion rate of
the organic compounds toward the gas bubbles and on the Henry
coefficient. In Figure 5, k1,0 is plotted versus the dimensionless
Henry coefficient (i.e., concentration in the gas phase (mol/L),
divided by the concentration in the water phase (mol/L), at
equilibrium) at 25 °C. Any relationship, if existing, is not very
clear. It may be argued that styrene is more reactive than
expected, due to polymerization. Benzene might be less reactive
than expected because it has no substituent on the aromatic ring.
Another way to determine the factor governing the partition-
ing between liquid and cavitations is by studying the parameter
a. This parameter indicates how efficient the compounds lower
the cavitation temperature during collapse. However, the
physicochemical properties of the reactive reaction products also
influence a, which complicates comparison. Figure 6 shows
parameter a vs the dimensionless Henry coefficient. Again,
there is no clear relationship. Contrarily, the only straight line
that falls within all confidence intervals, is a descending one.
These results suggest that diffusion limitations govern the
partitioning of the aromatic compounds between the liquid and
11640 J. Phys. Chem., Vol. 100, No. 28, 1996 De Visscher et al.

TABLE 4: Parameter Values after Regression (with 95% Confidence Intervals), Lack of Fit Standard Deviations, and
Correlation Coefficients
compd k1,0 (min-1) a (mM-1) f s (%) r
benzene 0.0271 ( 0.0016 0.996 ( 0.101 0.657 ( 0.175 6.1 0.999 (n ) 40)
ethylbenzene 0.0622 ( 0.0107 1.352 ( 0.458 0.065 ( 0.142 9.2 0.998 (n ) 22)
o-chlorotoluene 0.0431 ( 0.0072 0.828 ( 0.552 0.069 ( 0.286 7.3 0.998 (n ) 19)
styrene 0.0446 ( 0.0057 1.569 ( 0.28 0.309 ( 0.221 4.0 0.999 (n ) 23)

of the frequency of the ultrasonic waves on the sonolysis

process. The frequency has an influence on the resonance radius
of the cavitation. Bubbles larger than resonance size are not
assumed to collapse violently.28 Pétrier et al.12 assume that the
bubble collapse is most violent at resonance size. The resonance
frequency of a vibrating gas bubble is28

x
1 3γ(P0 + (2σ/R0))
νres ) (14)
2πR0 F

with R0 the bubble radius (m) at hydrostatic pressure P0 (Pa), γ

Figure 5. k1,0 vs dimensionless Henry coefficient at 25 °C (H benzene
and ethylbenzene from De Wulf et al.;20 H o-chlorotoluene estimated
from Schwarzenbach et al.;21 H styrene calculated from Willink32).
the specific heat ratio, σ the surface tension (N/m), and F the
density of the liquid (kg/m3). γ can be set equal to 1.33 for an
air-water vapor mixture,28 and σ equals 0.07 197 N/m for water
at 25 °C.22 Solving eq 14 for νres equal to 520 000 Hz yields
a resonant bubble radius of 6.77 µm; if νres equals 20 000 Hz,
the resonant bubble radius is 161 µm, 23.7 times as large. The
non-steady-state diffusion theory in spherical symmetry29 shows
that the equilibration time of a partitioning process is propor-
tional to the square of the sphere radius. Equation 17 in the
next paragraph confirms this. In the case of 20 kHz ultrasonic
waves, equilibration time for a resonant bubble will be more
than 560 times longer than in the case of 520 kHz ultrasonic
waves. Despite the longer cycle time, equilibrium between the
liquid phase and the bubble phase is harder to obtain with low-
frequency ultrasonic waves. This might explain why Bhatnagar
and Cheung8 did not find any deviations from first-order
kinetics. This might also explain why sonochemical degradation
is more efficient at high frequency.7

Estimation of the Organic Vapor Content of the

Cavitation Bubbles
During growth of a cavitation bubble, the organic molecules
diffuse into it. Since the growth time is very short, on the order
of 1 µs, the diffusion is restricted to a very thin liquid layer
surrounding the bubble. In this case planar geometry can be
assumed.
The concentration profile of a compound near an interface
of zero concentration is29

C ) Cl erf(z/(4Dlt)1/2) (15)

with C the concentration in the liquid boundary layer (mM )

Figure 6. a vs dimensionless Henry coefficient at 25 °C (H benzene mol/m3), Cl the bulk liquid concentration, z the distance from
and ethylbenzene from De Wulf et al.;20 H o-chlorotoluene estimated the bubble interface (m), Dl the diffusion coefficient (m2/s), and
from Schwarzenbach et al.;21 H styrene calculated from Willink32). t the time (s).
The flux F (mmol/(m2 s)) at the interface is
the cavitation bubbles. This is confirmed by calculations made
in the next paragraph. F ) SCl(Dl/πt)1/2 (16)

Comparison with Other Studies
The finding that the degradation rate of the compounds
decreases with increasing concentration is consistent with the
findings of Hart et al.,6 but such a behavior is not clear from
Bhatnagar and Cheung’s study.8
To compare the results presented above with the work of
Bhatnagar and Cheung,8 it is necessary to consider the influence
with S the interface surface (m2), which equals 4πR2, R being
the radius of the bubble.
Integrating the flux and dividing by the bubble volume yields
the concentration in the bubble as a function of time:
Cg ) (6/R)(Dlt/π)1/2Cl (17)
Taking Dl ) 1.2 × 10-9 m2/s for benzene at 29 °C,21 R ) 6.77
Sonochemical Breakdown of Aromatic Compounds
× 10-6 m (resonant size), t ) 0.96 × 10-6 s (half cycle30), and
a liquid concentration of 3.38 mol/m3, which is the highest
concentration used in the regression, a gas concentration of 5.74
× 10-2 mol/m3 is obtained. The saturated water vapor
concentration22 at 29 °C is 1.594 mol/m3, assuming ideal gas
behavior. The mole fraction of benzene in the bubble is 0.0347.
According to eq 15, the concentration reaches 99% of the
bulk concentration at a distance of 1.821(4Dlt)1/2, which equals
1.2 ×10-7 m, less than 2% of the bubble radius. The use of
planar geometry is justified.
Taking 0.229 for the dimensionless Henry coefficient of
benzene at 29 °C,20 the liquid concentration in equilibrium with
5.74 ×10-2 mol/m3 gas is 0.25 mM, about 7.4% of the bulk
concentration of benzene. The assumption of a zero interface
concentration is justified.
The specific heat ratio of benzene is 1.1.24 The term (γ1 -
1)x0 in eq A6 of Appendix A equals 0.09653; (γ0 - 1)x1 equals
0.01145, using 1.33 for the specific heat ratio of water. The
slope of γ vs x1 will change only slightly over 10% in the
concentration range used. This means that the linearization used
in eq A7 is justified.
In eq 8, another approximation is made, based on the low
value of KCl. Using the above values, and comparing eq A6
with eq 4, a value of 0.0244 is obtained at a liquid concentration
of 3.38 mM, about 7.4% of the term γ0 - 1. The approximation
is justified.
With the assumptions as above, the activation energy of the
reaction can be estimated using the definition of parameter a.
aRTPmax(γ0 - 1)2
E) (18)
KPmin
If Pmax is chosen equal to the hydrostatic pressure and Pmin equal
to the vapor pressure of water,28 this equation yields an
activation energy of 954 kJ/mol for benzene, about twice the
hydrogen-carbon bond strength in benzene (465 kJ/mol31).
According to eqs 3 and 4, the parameters used suggest a
temperature of 2521 K for the imploding cavitations in pure
water and a temperature of 2335 K in the presence of 3.38 mM
benzene. This is within the range obtained by Mišı́k et al.4
and by Hart et al.6 Therefore, it is assumed that the calculations
are reasonably accurate. According to these calculations, all
approximations made in the derivation of the reaction rate as a
function of temperature appear to be justified.
Conclusions
The sonochemical degradation of monocyclic aromatic com-
pounds can be described by a model, assuming that the presence
of the organic compounds lowers the temperature of the
collapsing cavitation bubble, by lowering the specific heat ratio.
It was necessary to account for the existence of reaction products
that also influence this temperature. A simple triangular reaction
scheme was used for this purpose. Despite the linearization
performed in order to simplify the model and the assumptions
made to limit the number of adjustable parameters, a good fit
was obtained. Lack of fit standard deviations ranged from 4 to
9.2%, and regression correlation coefficients were well over 0.99
in all cases. Correlations between the parameters and the Henry
coefficient are not clear, which suggests that partitioning of the
organic compounds between the liquid phase and the bubble
phase is mainly governed by the diffusion rate. Some brief
calculations support this assumption. The calculations also
confirm that the approximations made are justified. It can be
explained why deviations from first-order kinetics are less clear
in the case of 20 kHz ultrasound.
J. Phys. Chem., Vol. 100, No. 28, 1996 11641
List of Symbols
a exponential coefficient (mM-1)
A Arrhenius proportionality factor (min-1)
C concentration of organic compound in the vicinity of an interface
(mM)
Cg concentration of S in the bubble phase (mol/m3 ) mM)
Cl concentration in the liquid phase (mM)
Cl,1 concentration of S in the liquid phase (mM)
Cl,2 concentration of pseudospecies S + P in the liquid phase (mM)
cp specific heat at constant pressure (J/(mol K))
cp,0 specific heat of the air-water vapor mixture in the cavitation
bubbles, at constant pressure (J/(mol K))
cp,1 specific heat of the organic compound vapor at constant pressure
(J/(mol K))
cv specific heat at constant volume (J/(mol K))
cv,0 specific heat of the air-water vapor mixture in the cavitation
bubbles, at constant volume (J/(mol K))
cv,1 specific heat of the organic compound vapor at constant volume
(J/(mol K))
Dl diffusion coefficient in the liquid phase (m2/s)
E activation energy (J)
k first-order rate constant (min-1)
k0 first-order rate constant at infinite dilution (min-1)
k1 first-order rate constant of reactant S (min-1)
k1,0 first-order rate constant of reactant S at infinite dilution (min-1)
k2 first-order rate constant of pseudospecies S + P (min-1)
K proportionality factor (mM-1)
P0 hydrostatic pressure (Pa)
Ps solvent vapor pressure (Pa)
Pmax maximum pressure in the liquid during cavitation collapse (Pa)
Pmin minimum pressure in the bubble during rarefaction (Pa)
r reaction rate (mM min-1)
r1 reaction rate of reactant S (mM min-1)
r2 reaction rate of pseudospecies S + P (mM min-1)
R universal gas constant (8.314 J/(mol K)) or bubble radius (m)
R0 bubble radius at equilibrium with hydrostatic pressure (m)
S surface of bubble interface (m2)
t time (min or s)
T bulk liquid temperature (K)
Tc temperature of the cavitation during collapse (K)
x0 mole fraction of water vapor and air in the cavitation bubble
x1 mole fraction of the organic compound in the cavitation bubble
z distance from the bubble interface (m)
Greek Symbols
γ specific heat ratio of the gas-water-organic vapor mixture in
the cavitation bubble
γ0 specific heat ratio of the gas-water vapor mixture in the
cavitation bubbles
γ1 specific heat ratio of the organic vapor in the cavitation bubbles
νres resonance frequency of a cavitation bubble (s-1)
F liquid density (kg/m3)
σ surface tension (N/m)
Acknowledgment. A.D.V. wishes to thank the Vlaams
Impulsprogramma Milieutechnologie (VLIM) for financial
support. D.D. wishes to thank the Vlaams Instituut voor de
Bevordering van het Wetenschappelijk-Technologisch Onder-
zoek in de Industrie (IWT) for financial support.
Appendix A. Calculation of the Specific Heat Ratio of
Binary Gas Mixtures
The specific heat ratio γ is defined as
11642 J. Phys. Chem., Vol. 100, No. 28, 1996
cp
γ)
cv
with cp the specific heat at constant pressure (J/(mol K)) and cv
the specific heat at constant volume (J/(mol K)).
For ideal gases, the relation between cp and cv is
c p ) cv + R
with R the universal gas constant (8.314 J/(mol K)).
The specific heats of a gas mixture are
cp ) cp,0x0 + cp,1x1
cv ) cv,0x0 + cv,1x1
Subscript 0 refers to the air-vapor mixture in the cavitation of
pure water and is considered as a pseudospecies with mole
fraction x0. Subscript 1 refers to the organic compound, with
mole fraction x1. Substitution of eqs A3 and A4 in eq A1,
multiplying both numerator and denominator by R/(cv,0cv,1), and
substituting eqs A1 and A2, applied to both species, yields
γ0(γ1 - 1)x0 + γ1(γ0 - 1)x1
γ)
(γ1 - 1)x0 + (γ0 - 1)x1
γ can be written as a deviation from γ0:
-γ0(γ0 - 1)x1 + γ1(γ0 - 1)x1
γ ) γ0 +
(γ1 - 1)x0 + (γ0 - 1)x1
If x1 is sufficiently small, then x0 is almost equal to unity. In
that case, (γ1 - 1)x0 is much larger than (γ0 - 1)x1. Equation
A6 becomes
(γ0 - 1)(γ1 - γ0)
γ ) γ0 + x1
(γ1 - 1)
The factor [(γ0 - 1)(γ1 - γ0)/(γ1 - 1)] is a constant that will
be negative in the present case since the specific heat ratio of
aromatic compounds is smaller than the specific heat ratio of
water or air. If x1 is small, this factor will be proportional to
the liquid concentration of the organic compound. Therefore,
eq A7 can be written as
γ ) γ0 - KCl
References and Notes
(1) Suslick, K. S.; Hammerton, D. A.; Cline, R. E., Jr. J. Am. Chem.
Soc. 1986, 108, 5641.
De Visscher et al.
(2) Flint, E. B.; Suslick, K. S. Science 1991, 253, 1397.
(A1) (3) (a) Hiller, R.; Putterman, S. J.; Barber, B. P. Phys. ReV. Lett. 1992,
69, 1182. (b) Bernstein, L. S.; Zakin, M. R. J. Phys. Chem. 1995, 99, 14619.
(4) Mišı́k, V.; Miyoshi, N.; Riesz, P. J. Phys. Chem. 1995, 99, 3605.
(5) Hua, I.; Höchemer, R. H.; Hoffmann, M. R. J. Phys. Chem. 1995,
99, 2335.
(6) Hart, E. J.; Fischer, Ch.-H.; Henglein, A. Radiat. Phys. Chem. 1990,
36, 511.
(7) Lamy, M. F.; Pétrier, C.; Reverdy, G. Third meeting of the European
(A2) Society of Sonochemistry, Figueira da Foz, Portugal, 1993.
(8) Bhatnagar, A.; Cheung, H. M. EnViron. Sci. Technol. 1994, 28,
1481.
(9) Cheung, H. M.; Kurup, S. EnViron. Sci. Technol. 1994, 28, 1619.
(10) Makino, K.; Massoba, M. M.; Riesz, P. J. Am. Chem. Soc. 1982,
104, 5847.
(A3) (11) Atkinson, R. Chem. ReV. 1985, 85, 69.
(12) Pétrier, C.; Lamy, M.-F.; Francony, A.; Benahcene, A.; David, B.;
(A4) Renaudin, V.; Gondrexon, N. J. Phys. Chem. 1994, 98, 10514.
(13) Currell, D. L.; Wilheim, G.; Nagy, S. J. Am. Chem. Soc. 1963, 85,
127.
(14) Kotronarou, A.; Mills, G.; Hoffmann, M. R. J. Phys. Chem. 1991,
95, 3630.
(15) Kotronarou, A.; Mills, G.; Hoffmann, M. R. EnViron. Sci. Technol.
1992, 26, 1460.
(16) (a) Murali Krishna, C.; Lion, Y.; Kondo, T.; Riesz P. J. Phys. Chem.
1987, 91, 5847. (b) Murali Krishna, C.; Kondo, T.; Riesz, P. J. Phys. Chem.
1989, 93, 5166.
(17) Fitzgerald, M. E.; Griffing, V.; Sullivan, J. J. Chem. Phys. 1956,
25, 926.
(A5) (18) Griffing, V. J. Chem. Phys. 1952, 20, 939.
(19) Gutiérrez, M.; Henglein, A. J. Phys. Chem. 1988, 92, 2978.
(20) De Wulf, J.; Drijvers, D.; Van Langenhove, H. Atmos. EnViron.
1995, 29, 323.
(21) Schwarzenbach, R. P.; Gschwend, P. M.; Imboden, D. M. EnVi-
ronmental Organic Chemistry; J. Wiley & Sons: New York, 1993.
(22) Weast, R.; Astle, M. J.; Beyer, W. H. CRC Handbook of Chemistry
(A6) and Physics, 64th ed.; CRC Press: Cleveland, OH, 1983.
(23) Reid, R. C.; Prausnitz, J. M.; Pohling, B. E. The Properties of Gases
and Liquids, 4th ed.; McGraw-Hill: Singapore, 1988.
(24) Liley, P. E.; Reid, R. C.; Buck, E. In Perry’s Chemical Engineers’
Handbook, 6th ed.; Perry, R. H., Green, D. W., Eds.; McGraw-Hill:
Singapore, 1984.
(25) Riesz, P.; Kondo, T. Free Rad. Biol. Med. 1992, 13, 247.
(26) Hoerl, A. E.; Nashed, M. N.; McKetta, J. J.; Silberberg, I. H. In
Perry’s Chemical Engineers’ Handbook, 6th ed.; Perry, R. H., Green, D.
(A7) W., Eds.; McGraw-Hill: Singapore, 1984.
(27) Froment, G. F.; Hosten, L. H. In Catalysis: Science and Technol-
ogy; Anderson, J. R., Boudart, M., Eds; Springer-Verlag: Berlin, 1981;
Vol. 2.
(28) Shutilov, V. A. Fundamental Physics of Ultrasound. Ultrasonic
CaVitation; Gordon and Breach Science Publishers: New York, 1988.
(29) Crank, J. The Mathematics of Diffusion; Oxford University Press:
London, 1967.
(30) Assuming that the bubble collapses in the first cycle. This is usually
the case, as calculated by Church, C. C. J. Acoust. Soc. Am. 1988, 83, 2210.
(31) Streitwieser, A., Jr.; Heathcock, C. H. Introduction to Organic
Chemistry, 3th ed.; Macmillan Publishing Co.: New York, 1989.
(4) (32) Willink, T., Ed. Chemiekaarten: GegeVens Voor Veilig Werken met
Chemikaliën, 7th ed.; Nederlandse Vereniging van Veiligheidsdeskundigen,
Veiligheidsinstituut, Vereniging van de Nederlandse Chemische Industrie:
‘s Hertogenbosch, The Netherlands, 1991.
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