Chemical Engineering Science 64 (2009) 1635 -- 1642

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Chemical Engineering Science

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Modeling ultrasound-induced nucleation during cooling crystallization

Anna Kordylla a , Thomas Krawczyk a , Feelly Tumakaka b , Gerhard Schembecker a,∗
a
Laboratory of Plant and Process Design, Department of Biochemical and Chemical Engineering, Technische Universität Dortmund, Emil-Figge-Str. 70, D-44227 Dortmund, Germany
b
Laboratory of Thermodynamics, Department of Biochemical and Chemical Engineering, Technische Universität Dortmund, Emil-Figge-Str. 70, D-44227 Dortmund, Germany

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

Article history: A model to simulate cooling crystallization processes with ultrasound is proposed by introducing an
Received 22 August 2008 additional kinetic expression for nucleation mechanism due to the ultrasound irradiation. Applying the
Received in revised form 17 December 2008 model to predict the concentration profiles, nucleation rates, and crystal-size distribution during the
Accepted 19 December 2008
sonocrystallization process shows that the key parameter for understanding induced nucleation seems to
Available online 6 January 2009
be the reduction of the nucleation work, which verifies the assumption of a heterogeneous-nucleation
In memory of Anna Kordylla
mechanism. Hence, the specific foreign surfaces of the cavitation bubbles as well as the adsorption prop-
Keywords: erties of the forming crystals on the cavitation bubbles play important roles in qualitative prediction of
Crystallization the number of induced nuclei. Furthermore, enhanced diffusion due to ultrasonic waves seems to have a
Nucleation minor effect on the nucleation mechanism.
Mathematical modeling © 2009 Elsevier Ltd. All rights reserved.
Population balance
Simulation
Ultrasonic irradiation

1. Introduction agglomeration phenomena. Parallel to that, a starting point for the

Batch crystallization of organic compounds from solution is a
widely used unit operation in the production of pharmaceuticals,
pigments or polymers. There is a big need to obtain certain product
specifications during the process, such as good filterability, good
flow ability, low fines concentration and no caking on storage. These
specific properties mainly depend on the size of the crystals and
their size distribution as well as the crystal habit.
For the sake of finding an effective and precise way to control
crystallization processes a huge number of investigations was car-
ried out in the past decades. Besides controlling the supersaturation
in terms of the system temperature or adding seed crystals to the
supercooled solution, the use of ultrasonic irradiation has become an
interesting method to control the process as well as to influence the
size distribution and the habit of the crystalline product (Ruecroft
et al., 2005). Seeding and using ultrasound have in common that
they lead to a decay of the slurry concentration at lower levels of
supersaturation and consequently circumvent or at least affect the
hardly controllable primary nucleation at high supersaturations.
The initial characteristic of the supersaturation curve is deter-
mined by the following seeding parameters: number, size, and size
distribution of the seeds or the induced nuclei, respectively. More-
over, the seeding point has an important impact on the reduction of
the concentration in the mother liquor and therefore, on growth and
∗ Corresponding author. Tel.: +49 231 755 2339; fax: +49 231 755 2341.
E-mail address: gerhard.schembecker@bci.tu-dortmund.de (G. Schembecker).
application of ultrasound can also be specified (Kordylla et al., 2008).
All studies on the use of ultrasound in crystallization processes
agree in the statement that ultrasound of a sufficient energy level
reduces the metastable-zone width through an increased nucleation
rate (Li et al., 2006; Miyasaka et al., 2006). Nevertheless, these studies
led to different theories explaining why ultrasound induces primary
nucleation at a lower level of supersaturation compared to cooling
crystallization without the use of ultrasonic irradiation.
In most of the publications concerning the ultrasonic nucleation
phenomenon, cavitation induced by ultrasound plays a major role
(Guo et al. 2006a,b; Hem, 1967; Kim et al., 2003; Lyczko et al., 2002;
Virone et al., 2006). Hem (1967) gave an overview of assumptions
and argumentations concerning the impact of power ultrasound on
the crystallization process. Arguments whether the ultrasonic nucle-
ation phenomenon is of heterogeneous or homogeneous nature were
opposed. Furthermore, possible mechanisms such as cavitation, ag-
itation, cooling effect or an increased melting point were discussed.
He noted that the latter three cannot sufficiently explain the ultra-
sonic mechanism.
Virone et al. (2006) assumed that high pressures in cavities as
bubbles collapse during ultrasonic irradiation lead to an increased
driving force. They applied the classical theory for homogenous nu-
cleation and calculated the nucleation rates under this assumption.
However, they could not reproduce their experimental results with
the estimated nucleation rates. Lyczko et al. (2002) proposed that
ultrasound changes the activation energy and therefore, according
to the heterogeneous nucleation approach, either the surface energy
for the crystal-solution interface or the wetting angle.

0009-2509/$ - see front matter © 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2008.12.030
1636 A. Kordylla et al. / Chemical Engineering Science 64 (2009) 1635 -- 1642
Kim et al. (2002) used ultrasonic irradiation continuously
throughout the process instead of mechanical stirring and in-
vestigated the development of the crystal-size distribution (CSD)
experimentally and theoretically. For the re-crystallization of an
insensitive explosive with ultrasonic insonation the CSD turned out
to be much narrower than without the use of ultrasound. The ki-
netics of nucleation and growth were expressed in terms of simple
power-laws. The difference between the mechanical stirred system
and ultrasound was considered only by different pre-factors for both
phenomena. The orders of these kinetic laws were kept constant.
In the case of a short ultrasound burst in the discrete interval
between the saturated state and the metastable limit it is infeasi-
ble to quantitatively interpret the effects based on the reduction of
the induction time alone. The simplification to consider the induc-
tion time to be inversely proportional to the nucleation rate is based
on the assumption of one specific nucleation mechanism neglecting
the dependency of coinciding or following growth and nucleation
processes on the supersaturation. Growth of the generated crystals
associated for instance has an impact on the supersaturation pro-
file and thus on the driving force for secondary nucleation, further
also on growth and agglomeration. Since the superposition of these
kinetic phenomena involved is decisive for the progress of the pro-
cess, accurate modeling is needed especially to reflect the influence
of the applied ultrasound and to distinguish between the influences
mentioned above.
In general, numerous different crystallization models can be
found in the literature mainly based on the formal approach of a
population balance, which provides an opportunity to reflect the
progression of CSD (Marchal et al., 1988). Most of the models for
seeded batch crystallization processes deal with the objective to
optimize the product specifications through the use of an adapted
temperature profile (Worlitschek and Mazzotti, 2004).
Hu et al. (2005) gave an overview concerning models for seeded
batch crystallization processes and pointed out that most of the
optimized temperature profiles resulted from reduced population-
balance models using the method of moments. Due to this fact, they
are limited to the case of size-independent growth rates and a model
was developed which directly solved the population balance equa-
tions without reducing them to a set of ordinary differential equa-
tions.
Recently, Oullion et al. (2007a,b) presented a new approach to
model a seeded crystallization process. They used a bi-dimensional
population balance to track two characteristic lengths of plate-like
crystals and investigated the influence of the seeding temperature,
cooling rate, and total area of the seed particles.
So far, no literature was found describing the crystallization
with ultrasound in terms of physical-based parameters. Hence, the
objective of this work is to comprehend the mechanism of induced
nucleation by ultrasound and to evaluate an optimized application
of ultrasound aiming on the desired product specifications. There-
fore, a crystallization model was developed using a one-dimensional
population balance considering an additional kinetic expression for
ultrasound-induced nucleation mechanism among the mechanisms
for primary nucleation and secondary nucleation using physical
properties rather than model parameters.
The paper is organized as follows: The modeling of a batch crys-
tallization process via a population balance is introduced shortly.
Afterwards, the kinetic expressions implemented for primary and
secondary nucleation and growth during the normal cooling crys-
tallization are presented. Using this model an approach for the ul-
trasonic nucleation phenomenon is derived. Concentration profiles,
nucleation rates and CSD predicted by the model are compared with
experimental results and discussed. Possible additional process pa-
rameters are then identified, which have to be taken into account
during further investigations.
2. Modeling
2.1. Population balance
The population-balance approach offers a possibility to describe
the variations of sizes of dispersed systems as function of time. A
population balance associated with kinetic models and mass bal-
ance equations tracks the number-density distribution (n) at each
time step along the axes of the so-called internal and external co-
ordinates. The internal coordinate vector includes not only primer
characteristic sizes but also chemical activity or particle age, etc. in-
dependent of its position. Depending on the number N of the con-
sidered internal derivations the population balance is referred to as
N-dimensional. The considered process can be presented through a
one-dimensional population balance, if the growth of crystals G is
assumed to be independent of the crystal size L.
The external coordinate vector refers to spatial variations inside
the crystallizer. Assuming a perfectly mixed tank and therefore ne-
glecting concentration and temperature gradients, the crystallization
process can be described by the solution of one partial differential
equation. Combining hydrodynamic simulations with the solution of
a population balance for each volume element may be needed to be
obtained for the simulation of an up-scaled crystallization process in
the case the assumption of a perfectly mixed tank cannot be applied.
Based on the observations made during the experimental work
this paper is based on, nucleation and growth are the prevailing
mechanisms.
Under the assumptions listed above the population balance pro-
posed by Randolph and Larson (1988) for batch crystallizer can be
expressed as
jn jn
+G· + B(L) = 0 (1)
jt jL
The term jn/ jt represents the change in number density with respect
to time in the batch crystallizer, G is the growth rate, and the birth
rate B(L) is given as function of the sum of primary and secondary
nucleation rate J:
B(L) = J = Jprim + Jsec (2)
The implementation of the kinetic expressions for nucleation and
growth leads to a highly non-linear model, which is challenging to
resolve for many common solution methods. Due to this fact the
high resolution scheme published by Qamar et al. (2006) was used
to solve the resulting population-balance equations. This method is
a finite volume scheme, which subdivides the internal variable in
equidistant intervals. Usage of so-called flux limiters provides the
possibility to map sharp peaks and discontinuities. For more detailed
information on high resolution schemes the reader is referred to
Quamar et al. (2006) and references therein.
2.2. Crystallization kinetics
In order to reach equilibrium the concentration of the solute is
decreased through the generation of a new solid phase by first nu-
cleation and subsequent growth. Driving force for both processes is
the current supersaturation of the system which is given by the dif-
ference of the chemical potentials between the solute and the crys-
talline substance. In this work this driving force is assumed to be
proportional to the ratio of the concentration in the bulk phase c to
the equilibrium concentration c∗ :
c
 = kB T ln S = kB T ln (3)
c∗
 A. Kordylla et al. / Chemical Engineering Science 64 (2009) 1635 -- 1642 1637

with kB the Boltzmann constant and T the temperature, respectively. The pre-factor  is a function of the wetting angle of the cluster
The supersaturation ratio S can be also expressed in term of the onto the foreign surface.
relative supersaturation  defined as
(2 + cos )(1 − cos )2
=S−1 (4) ( ) = (10)
4
If the solution is free of foreign particles and surrounding surfaces, The stationary primary nucleation rate can be calculated under the
the generation of the new solid phase undergoes the homogeneous assumption of a Boltzmann distribution of the cluster sizes, which
mechanism. However, in most of the cases existing foreign parti- are given by their total energy G∗het by the following equation
cles promote the nucleation; this mechanism is referred to as het- (Kashchiev and van Rosmalen, 2003):
erogeneous nucleation. Both mechanisms are grouped into the term  
“primary” nucleation. In contrast to that, the nucleation initiated due ∗
−G∗het
Jprim = z · k · C0 exp (11)
to existing native crystals is called secondary nucleation. Further- kB T
more, secondary nuclei can either be generated through mechanical
abrasion or through thermodynamical effects. The Zeldovich factor z considers the difference between the steady-
state and the equilibrium distribution of the critical clusters, which
2.2.1. Kinetic expressions for primary nucleation can be calculated as
Considering first the primary homogeneous nucleation, the clas- 
sical theory describes the nucleation as successive attachments and G∗het
z= (12)
detachments of molecules or monomers to form the so-called clus- 3 · kB T · n∗2
ters of different sizes according to Volmer and Weber (Kashchiev and
van Rosmalen, 2003). The work, which is necessary to form a cluster The factor k∗ considers the monomer attachment frequency either
of n monomers or molecules, respectively, is given by the difference for a diffusion or for an integration controlled uptake of monomers.
between the free energy of the system in its final and initial state. In this work, the diffusion controlled frequency factor k∗ is chosen
During the cluster formation the superposition of two competitive and given by
energy terms, namely the positive free-surface enthalpy and the neg-
ative free-volume enthalpy leads to a maximum, which represents k∗ = (48 · 2 ·
0 )1/3 · D · c · NA · n∗1/3 (13)
the energy barrier for nucleation. A cluster at this energy barrier is
The diffusion coefficient D is calculated using the Stones–Einstein
called critical cluster or nucleus. The work to form clusters of crit-
equation as a function of temperature, dynamic viscosity , and
ical size, the so-called nucleation work is given by the relationship
molecular diameter dm as proposed by Mersmann (2001):
(Kashchiev and van Rosmalen, 2003):

16 ·  · 20 · 3 kB T
D= (14)
G∗hom = (5) 2 ·  · dm
3 · (kB T)2 ln2 S
In the case of a heterogeneous mechanism C0 represents the nucle-
where 0 is the molecular volume of the crystal, which can be calcu-
ation sites on the foreign surface, whereby it can be calculated under
lated from the molar mass of the solute and the density of the solid
certain assumptions by the product of the specific surface area of the
phase according to Eq. (6), and  the interfacial tension, respectively,
foreign surface afor and the adsorption properties Head according to
M
0 = (6) C0 = afor · Head · c · dm · NA
C · NA (15)

The interfacial tension is a decisive property parameter in crystalliza- The foreign surface can be supplied by suspended particles, sur-
tion processes, which cannot be measured with a sufficient accuracy rounding surfaces like the wall of the crystallizer or a second fluid
and without any overlapping effects. It was proposed in Kashchiev phase like bubbles or drops. Since C0 depends on the specific surface
and van Rosmalen (2003) to apply the following empirical equation: area and the adsorption properties of the cluster onto the foreign
  surface which are not experimentally accessible, C0 was treated as
k T c
 = K · B2 ln c with 0.2 < K < 0.6 (7) an adjustable parameter in the modeling.
dm c

with dm as the molecular diameter of the crystal, cc the molar con-
centration of the crystals, and c the molar concentration in the bulk
phase, respectively. The pre-factor K was set to 0.514 in this work,
which corresponds to spherical clusters.
Nuclei consist of a critical number of monomers n∗ which can be
estimated by the following relation:
32 ·  · 20 · 3
n∗ =
3 · (kB T)3 ln3 S
Turning now to the heterogeneous mechanism, the nucleation work
is decreased since foreign surfaces reduce the free-surface enthalpy
and consequently act as nucleation sites. The reduction of the nucle-
ation work by foreign particles is commonly accounted for by a pre-
factor for the interfacial tension, which is equivalent to a reduced
nucleation work according to Mersmann (2001) or Mullin (2001):
eff = 1/3 ( ) ⇔ G∗het = ( )G∗hom
2.2.2. Kinetic expressions for secondary nucleation
Secondary nucleation occurs if crystals of the same substance al-
ready exist and induce new nuclei. There are two main mechanisms
how secondary nuclei can be generated: either by a thermodynamic
mechanism (surface secondary nucleation, SSN) or by a mechani-
cal mechanism (contact secondary nucleation, CSN). The thermody-
namic mechanism occurs due to the presence of crystals of the same
substance, while no fluid dynamic is necessary. The number of nu-
(8)
clei formed is sensitive to the surface area of the crystals present
and can be obtained as
 
 
D  · dm 2 1
SSN
Jsec = e · ac · 4 exp − · (16)
dm kB T ln S
The efficiency factor e gives the probability of the surface nucleation,
which is treated as an adjustable parameter in the modeling, and
ac is the specific volumetric surface of existing crystal, respectively,
(9) which is expressed by the second moment of the CSD.
1638 A. Kordylla et al. / Chemical Engineering Science 64 (2009) 1635 -- 1642

Further nucleation takes place because crystals break due to col-

lision with the stirrer. These nuclei, which can be calculated by the primary nucleation nucleation growth
kinetic due to kinetics
following empirical relationship of the crystal number with three primary & secondary kinetics
the initiation
adjustable parameters kN , n, CSN, and k, CSN (Garside, 1985):
nucleation nucleation growth
rate Jinit rate J rate G
CSN
Jsec = kN ·  n,CSN k,CSN
(c · NA ) (17)

The total of secondarily formed nucleation rate is hence population balance

SSN CSN
Jsec = Jsec + Jsec (18) Ni(t=0) Ni(t=t) Ni(t=tend)

2.2.3. Kinetic expressions for crystal growth crystal number distribution

In this study the relationship between the crystal growth rate mass balance
and the driving force is described through the superposition of an concentration in the mother liquor
approach in the form of the Burton–Cabrera–Frank (BCF) model for super saturation
low supersaturation ratio and in the form of the birth-and-spread
(B&S) model for high supersaturation ratio (Mersmann, 2001).
Fig. 1. Scheme of the model presenting an initiated crystallization process.

G = GBCF + GB&S (19)

Following the model of continuously occurring screw dislocations 2.3. Nucleation due to insonation
the relationship between the growth rate and the supersaturation
can be expressed as follows: In order to describe the cooling crystallization initiated by a short
ultrasound burst, an extended nucleation approach has to be taken
BBCF
GBCF = ABCF · 2 · tanh (20) into account additionally to the model presented in the previous
 section. The approach has only validity during the short burst and
The B&S model proposes nucleation on the crystal surface and there- replaces the normal nucleation mechanism for this time, for in-
fore subsequent growth: stance 30 s. In accordance to the experimental results in Kordylla
et al. (2008), nuclei formed due to the cavitating bubbles when ul-
 
BB&S trasound was applied are considered by a heterogeneous approach.
GB&S = AB&S · p,B&S exp (21)
 Fig. 1 shows the scheme of the proposed model for crystallization
process with extension due to the nucleation step caused by the us-
For both growth-rate approaches the deeper meaning of the param- age of the initiation method.
eters A and B are not considered in this work and these therefore The ultrasonic nucleation mechanism during the ultrasound burst
represent adjustable parameters. is represented through the following approach:
 
−G∗init
2.2.4. Mass balance equations Jinit = z · k∗ · C0,init exp (26)
Since the population balance includes variables which are func- kT
tions of the current supersaturation, a mass balance has to be solved
simultaneously to determine the number concentration of bulk C, The Zeldovich factor z and the frequency factor k∗ were taken from
and the number concentration of the solid phase Cc , respectively. Eqs. (12) and (13), respectively. The initiated nucleation work can be
The overall mass balance reads (Oullion et al., 2007a) expressed by means of Eq. (5) with the corresponding interfacial ten-
sion. As the specific surface area of the bubbles and the adsorption
d[Vsol (t)C(t) + Vsus (t)Cc (t)] properties of the forming cluster for induced nucleation are differ-
=0 (22) ent from the not-initiated case, the parameters C0 and C0,init could
dt
differ in both of the cases. The nucleation work is reduced, which
While the total volume of the suspension Vsus is assumed to be con- can be either due to a lower wetting angle between the cluster and
stant, the variation of volume of the solution Vsol due to the gener- the bubble surface area or due to the induced energy of ultrasonic
ation of a solid phase can be obtained by the following equation: waves, which decrease the activation energy and therewith the crit-
ical cluster radius, as it is already pointed out in Lyczko et al. (2002).
mc
Vsol = Vsus − (23)
c
3. Simulation and comparison with experimental results
The crystalline mass/magma density is given by the third moment
of the distribution. In practice the discrete form is used: 3.1. Experimental cooling crystallization in silent condition
3
Cc (t) = c ·  · Lj · Nj (t) (24) The simulation results will be compared with experimental data
j taken from Kordylla et al. (2008). Cooling crystallization of dode-
canedioic acid (DDDA, C12 H22 O4 ) from propyl acetate was performed
where  is a volumetric shape factor, which relates the volume of with a rate of 0.5 ◦ C/min in a double jacketed 1.2 L glass reactor.
sphere to the one of a cube with length L. The concentration C(t) of The solubility in [g/g solution] as a function of temperature can be
solute can be established for every time point by the expression expressed by the following empirical relation valid in the range be-
tween 10 and 60 ◦ C:
C0 V0 − Cc (t) · Vsus
C(t) = (25) −2
Vsol (t) c∗ = 5.722 × 10−4 × e6.45×10 T
(27)
 A. Kordylla et al. / Chemical Engineering Science 64 (2009) 1635 -- 1642 1639

Determination of γeff at Smax =1.8 Table 1

Parameters used to describe the crystallization process in silent condition.

Primary nucleation Secondary nucleation Growth

1. γeff 0.0005 – 0.0009 J/m2
◦
45 kN 0.003 ABCF 0.6
C0 1021 n, CSN 2.49 BBCF 2
k, CSN 0.89 AB&S 1000
Calculation of γ (empirical equation) e 6.10−11 BB&S 5
pB&S 0.9

2. γ 0.010 – 0.014 J/m2

Calculation of θ from γeff = γ ψ(θ)

3. θ 35° – 50°

Fig. 2. Procedure of parameter determination in the primary nucleation term.

3.2. Simulation of cooling crystallization in silent condition

The procedure to determine the parameters [ , C0 , e, kN , n,CSN ,

k,CSN ; ABCF , BBCF , AB&S , BB&S , pB&S ] was carried out as follows: The max-
imum of the supersaturation curve during the crystallization process
is mainly determined by primary nucleation. As an effective inter-
facial tension for first simulation runs was used, the primary nu-
cleation mechanism is not yet specified. Whether the implemented
approach for this primary nucleation step is either of heterogeneous
Fig. 3. Simulated (line) and measured concentration profile (symbols) for the cooling
or homogeneous nature is merely considered by the magnitude of crystallization of dodecanedioic acid from solution with propyl acetate.
the parameters and C0 , respectively.
In the crystallization process the subsequent growth and sec-
ondary nucleation affect the decay of the slurry concentration and
growing crystal, while the generation of nuclei via the SSN mech-
consequently also the maximum of the supersaturation. As is shown
anism is limited to a certain range of supersaturation. Beyond this
by the experimental results it can be assumed in this work that
range, primary nucleation dominates.
growth and secondary nucleation play a minor part. The character-
The parameters to be identified for the kinetic approach regarding
istic of the supersaturation and slurry concentration depends more
the crystal growth rate are rather model parameters than physical
on the primary nucleation step than on the subsequent growth and
properties. In the region of lower supersaturations the mechanism
secondary nucleation.
was assumed to proceed mainly according to the model of BCF. While
Fig. 2 shows schematically the procedure to determine the de-
in this region the approach of the B&S model predicts a vanishing
cisive parameters for the primary nucleation step occurring during
growth rate, it is the prevailing part for higher supersaturations.
cooling crystallization in silent condition. In order to match the max-
After the identification of the specific ranges for each parameter,
imum supersaturation ratio found in the experiment (Smax = 1.8), C0
the following objective function was used to determine the combi-
was set to 1021 , and the effective interfacial tension eff was deter-
nation of parameters, which present the experimental results in the
mined by fitting the supersaturation maximum of the simulation to
best way. The objective function was taken from the work of Oullion
the one observed in the experiment which resulted in a value in the
et al. (2007a):
range between 0.5 × 10−3 and 0.9 × 10−3 J/m2 . Since the interfacial
tension is not measurable with a sufficient accuracy, it is calculated ⎛ ⎞
 exp 2
using the semi-empirical equation (7). A comparison of the effective ⎜
exp sim 2 ⎟
l − sim
l
fobj = ⎝ (C −C ) ⎠+  exp (28)
interfacial tension obtained by simulation and the calculated one l
shows that the calculated interfacial tension is higher by more than k=1, ...,n i=1, ...,n l=1, ...,n
an order of magnitude. The only way to explain this difference ex-
The parameter combination determined is shown in Table 1 and
ists in the value of the pre-factor in Eq. (10), which is a function of
leads to the concentration profile for the not-initiated crystallization
the wetting angle. Considering a heterogeneous mechanism, the in-
process shown in Fig. 3 and the CSD at the end of the process shown
terfacial tension calculated has to be reduced in accordance with a
in Fig. 4. The simulation results were compared to the experimental
reduced nucleation work due the adsorption of forming crystals on
data of cooling crystallization of dodecanedioic acid from propyl-
the foreign surface, which is taken into account by Eq. (9). The calcu-
acetate solution.
lated interfacial tension was reduced by a factor of  ( )=0.02–0.08,
which in reverse implies a wetting angle of about 35–50◦ .
Secondary nucleation was considered to occur in two mecha- 3.3. Experimental insonated cooling crystallization
nisms as presented in the previous section. For the SSN approach the
parameter e had to be identified, which considers the number of nu- In the region between the saturated state and the metastable
clei formed proportional to the surface area of the crystals present. limit power ultrasound was applied. Duration and levels of super-
CSN leads to a generation of new entities at a later point of saturation at start of insonation were varied. Frequency and nominal
the progressing crystallization due to breaking dendrites from the power of the ultrasound device, which mainly affect the efficiency
1640 A. Kordylla et al. / Chemical Engineering Science 64 (2009) 1635 -- 1642
Fig. 4. Experimental-determined crystal-number distribution at the end of the crys-
tallization process of dodecanedioic acid from solution with propyl acetate (symbols)
and comparison with simulation result (line).
of the generation of cavitating bubbles, were kept constant at a fre-
quency of 355.5 kHz and a nominal power of 200 W.
First experimental investigations on ultrasound showed that by
plotting the relative induction time against the supersaturation ratio
at the time insonation was started two regions can be determined:
For low supersaturation the induction time is inversely proportional
to the time point when it is applied. For higher supersaturation a
much lower dependency on the initial driving force was observed,
although this supersaturation still lies well below the metastable
limit. A transition between these ranges could be identified around
a supersaturation of 1.2 (Kordylla et al., 2008). Furthermore, it was
observed that the CSD from this transition point differs significantly
from the distributions for a lower initial supercooling during in-
sonation. This change could be explained as follows: For low super-
saturation insonation cannot reduce the nucleation work so much
that the energy barrier can be passed and nucleation can occur. Be-
yond the transition point, the energy barrier can be passed by ap-
plying ultrasound and nucleation can be induced since the critical
cluster radius and therewith the number of nuclei depends on the
nucleation work.
3.4. Simulation of insonated cooling crystallization
In our successive paper we will report experimental results which
will show that there have to be a significant reduction of the nucle-
ation work also due to the bubble surface area during gassing. Hence,
it can be assumed that the primer argument, namely the wetting an-
gle of the forming cluster onto the bubbles, plays an important role
regarding to the ultrasonic nucleation phenomenon.
While the parameters found for the kinetic processes during the
not-initiated cooling crystallization were kept constant, it turned out
that the additional parameter C0,init (the concentration of nucleation
sites in case of insonation) has small impact on the concentration
profile and CSD. Hence, the value for C0,init was taken from the cooling
crystallization without ultrasound, whereas the additional parameter
in the induced nucleation was fitted to the value of 27◦ , which
led to a reduction of the induction time in the range of medium
initial supersaturation ratio of about 1.22, corresponding to an initial
temperature of 35.7 ◦ C.
Fig. 5 shows the simulated concentration profiles of insonated
cooling crystallization of dodecanedioic acid from propyl-acetate
Fig. 5. Simulated concentration profiles during cooling crystallization of dodecane-
dioic acid from propyl-acetate solution with the application of ultrasound at differ-
ent initial supersaturations.
solution at starting concentration of 0.007 g/g solution. The ultra-
sound burst was applied for 30 s at different supersaturation-ratio
values of 1.05, 1.22, and 1.40, corresponding to initial temperatures
of 38, 35.7, and 33.6 ◦ C, respectively. For the sake of completeness,
the concentration profile of the cooling crystallization in silent con-
dition is depicted too, which is almost similar to the case, where the
ultrasound is applied at supersaturation value of 1.05. It can be seen
that when the ultrasound generator was turned on at too low initial
supersaturation value of 1.05, the concentration decay was much
slower, which indicated that no nucleation was induced by ultra-
sonic irradiation, whereas the other two concentration profiles for
two different initial supersaturation of 1.22 and 1.40 show that the
concentration decreases earlier and the profiles are steeper, which
proves the influence of the induced nucleation by ultrasound on the
initial supersaturation point.
At initial supersaturation ratio of 1.40 the resulting crystals are
smaller than 20 m. Hence, the concentration decay can be explained
only by high nucleation rate and crystal growth is less important for
the supersaturation depletion in this case—compared to other initial
supersaturations—as is shown in Fig. 6.
Therein, the CSD at the end of the sonocrystallization process
for different initial temperatures as well as for silent condition are
depicted. For an initial supersaturation-ratio value of 1.40 the me-
dian of the crystals was determined to be d50 = 4 m, compared to
d50 =352 m for initial supersaturation ratio of 1.22, and d50 =325 m
for initial supersaturation ratio of 1.05, the latter is identical to the
case of silent condition. Furthermore, narrow CSD was calculated for
the medium initial supersaturation of 1.22, which was also observed
experimentally (Kordylla et al., 2008). The comparison of the simu-
lated and experimental CSD width in term of d90 –d10 for insonated
cooling crystallization at different initial supersaturations is depicted
in Fig. 7. It can be concluded that induced nucleation by ultrasound
can be reproduced qualitatively by the proposed model.
Comparison of the experimental and theoretical investigations
on the sonocrystallization of dodecanedioic acid show that the im-
plemented heterogeneous approach predicts a higher dependency of
the nucleation rate on the initial supersaturation ratio as it is found
in the experiments.
Concluding the comparison of simulation runs carried out in this
work, the experiments presented in Kordylla et al. (2008) and based
on the assumption of a heterogeneous nucleation approach it can
be disproved that the ultrasonic nucleation phenomenon can be
 A. Kordylla et al. / Chemical Engineering Science 64 (2009) 1635 -- 1642 1641

Further theoretical and experimental investigations on the ultra-

sonic nucleation phenomenon may help to separate the influences of
the diffusion of monomers, the specific foreign surface as well as the
adsorption properties of the forming crystals by the aid of parallel
and contrary aspects due to the use of ultrasound to induce nuclei.

4. Conclusions

An approach to model nucleation induced by power ultrasound

during crystallization is developed in this work. The approach is
based on the assumption of heterogeneous nucleation mechanism:
During the ultrasound burst, an extended nucleation kinetic expres-
sion is applied. The simulation results show a qualitative agreement
with the experimental observations: An optimal condition of using
ultrasound during crystallization to achieve a narrow CSD turns out
to depend strongly on the supersaturation ratio at which the ultra-
sound is applied.

Fig. 6. Simulated crystal-number distributions at the end of the crystallization

process of dodecanedioic acid from solution with propyl acetate with the application Notation
of ultrasound at different initial supersaturations.

Symbols
ac specific volumetric surface, m2 /m3
B birth rate, 1/m3 /s
c concentration, mol/m3 , g/g
c∗ equilibrium concentration, mol/m3 , g/g
cc molar concentration of crystal, mol/m3
C number concentration, 1/m3
C0 number concentration of nucleation centers, 1/m3
dm molecular diameter of crystal, m
D diffusion coefficient, m2 /s
e efficiency factor, dimensionless
fobj objective function, dimensionless
G growth rate, m/s
G nucleation work, J/mol
He adsorption constant, dimensionless
J nucleation rate, 1/m3 /s
kB Boltzmann constant, J/K
k∗ collision factor, 1/s
K pre-factor for interfacial-tension calculation,
dimensionless
Fig. 7. Comparison of experimental-determined crystal-size-distribution widths L crystal size, m
(symbols) at the end of batch run of dodecanedioic acid in propyl acetate with M molar mass, g/mol
different initial supersaturations, at which the ultrasound is applied, to simulation n number density, 1/ m
results (lines).
n∗ number of monomers for critical nuclei, 1/s
NA Avogadro number, 1/mol
N crystal number, 1/m3
interpreted by an enhanced diffusion due to ultrasonic waves (Guo S supersaturation ratio, dimensionless
et al., 2006b). Moreover the modeling of the initiated crystalliza- t time, s
tion process shows that a reduction of the nucleation work is the T temperature, ◦ C, K
key parameter for the understanding of the ultrasonic nucleation V volume, m3
phenomenon. Concerning the parameters, the ultrasonic nucleation z Zeldovich factor, dimensionless
phenomenon cannot be justified only through an increased diffusion
introduced by the ultrasound alone. An enhanced diffusion can also Greek letters
be taken into account by increasing the parameter C0 , while keeping
the wetting angle and the interfacial tension constant. But to pre-  interfacialtension, J/m2
dict a plausible number of induced nuclei, the parameter C0 has to  driving force, J/mol
be more than 10 orders of magnitude higher than the one used for  dynamic viscosity, Ns/m2
the not-initiated case. A higher mass transfer of monomers to the wetting angle, ◦
forming cluster through the enhancement of diffusion cannot be the  density, g/m3
explanation of the ultrasound phenomenon. Nevertheless the argu-  relative supersaturation, dimensionless
ment of influencing the diffusion by the application of ultrasound 0 molecular volume of crystal, m3
may play a decisive role, as it may explain the lower nucleation rate  volumetric shape factor, dimensionless
for higher supersaturations due to a diffusion barrier. ( ) pre-factor for heterogeneous nucleation, dimensionless
1642 A. Kordylla et al. / Chemical Engineering Science 64 (2009) 1635 -- 1642

Sub- and superscripts Kashchiev, D., van Rosmalen, G.M., 2003. Review: nucleation in solutions revisited.
Crystal Research and Technology 38, 555–574.
ad adsorption Kim, S.J., Wei, C.K., Kiang, S., 2003. Crystallization process development of an active
c crystal pharmaceutical ingredient and particle engineering via the use of ultrasonics
and temperature cycling. Organic Process Research & Development 7, 997–1001.
eff effective Kim, Y.H., Lee, K., Koo, K.K., Shul, Y.G., Haam, S., 2002. Comparison study of mixing
exp experiment effect on batch cooling crystallization of 3-nitro-1,2,4-triazol-5-one (NTO) using
for foreign surface mechanical stirrer and ultrasound irradiation. Crystal Research and Technology
37, 928–944.
het heterogeneous Kordylla, A., Koch, S., Tumakaka, F., Schembecker, G., 2008. Towards an optimized
hom homogeneous crystallization with ultrasound: effect of solvent properties and ultrasonic
i component i process parameters. Journal of Crystal Growth 310, 4177–4184.
Li, H., Li, H.R., Guo, Z.C., Liu, Y., 2006. The application of power ultrasound to reaction
init initiated crystallization. Ultrasonics Sonochemistry 13, 359–363.
j interval j Lyczko, N., Espitalier, F., Louisnard, O., Schwartzentruber, J., 2002. Effect of ultrasound
m molecular on the induction time and the metastable zone widths of potassium sulphate.
Chemical Engineering Journal 86, 233–241.
obj objective
Marchal, P., David, R., Klein, J.P., Villermaux, J., 1988. Crystallization and
prim primary precipitation engineering. 1. An efficient method for solving population balance
sec secondary in crystallization with agglomeration. Chemical Engineering Science 43, 59–67.
Mersmann, A., 2001. Crystallization Technology Handbook. second, rev. and expanded
sim simulation
ed.. Marcel Dekker, New York.
sol solution Miyasaka, E., Takai, M., Hidaka, H., Kakimoto, Y., Hirasawa, I., 2006. Effect of ultrasonic
sus suspension irradiation on nucleation phenomena in a Na2 HPO4 · 12H2 O melt being used as
a heat storage material. Ultrasonics Sonochemistry 13, 308–312.
Abbreviations Mullin, J.W., 2001. Crystallization. fourth ed.. Butterworth, Heinemann, Oxford.
Oullion, M., Puel, F., Fevotte, G., Righini, S., Carvin, P., 2007a. Industrial batch
BCF Burton, Cabrera, Frank crystallization of a plate-like organic product. In situ monitoring and 2d-csd
modelling. Part 2: kinetic modelling and identification. Chemical Engineering
B&S birth and spread
Science 62, 833–845.
CSN contact secondary nucleation Oullion, M., Puel, F., Fevotte, G., Righini, S., Carvin, P., 2007b. Industrial batch
SSN surface secondary nucleation crystallization of a plate-like organic product. In situ monitoring and 2d-
csd modelling: part 1: experimental study. Chemical Engineering Science 62,
820–832.
References Qamar, S., Elsner, M.P., Angelov, I.A., Warnecke, G., Seidel-Morgenstern, A., 2006. A
comparative study of high resolution schemes for solving population balances
Garside, J., 1985. Industrial crystallization from solution. Chemical Engineering in crystallization. Computers & Chemical Engineering 30, 1119–1131.
Science 40, 3–26. Randolph, A.D., Larson, M.A., 1988. Theory of Particulate Processes: Analysis and
Guo, Z., Jones, A.G., Li, N., 2006a. The effect of ultrasound on the homogeneous Techniques of Continuous Crystallization. second ed.. Academic Press, San Diego.
nucleation of baso4 during reactive crystallization. Chemical Engineering Science Ruecroft, G., Hipkiss, D., Ly, T., Maxted, N., Cains, P.W., 2005. Sonocrystallization:
61, 1617–1626. the use of ultrasound for improved industrial crystallization. Organic Process
Guo, Z., Jones, A.G., Li, N., 2006b. Interpretation of the ultrasonic effect on induction Research & Development 9, 923–932.
time during baso4 homogeneous nucleation by a cluster coagulation model. Virone, C., Kramer, H.J.M., van Rosmalen, G.M., Stoop, A.H., Bakker, T.W., 2006.
Journal of Colloid and Interface Science 297, 190–198. Primary nucleation induced by ultrasonic cavitation. Journal of Crystal Growth
Hem, S.L., 1967. Effect of ultrasonic vibrations on crystallization processes. 294, 9–15.
Ultrasonics 5, 202–207. Worlitschek, J., Mazzotti, M., 2004. Model-based optimization of particle size
Hu, Q., Rohani, S., Jutan, A., 2005. Modelling and optimization of seeded batch distribution in batch-cooling crystallization of paracetamol. Crystal Growth &
crystallizers. Computers & Chemical Engineering 29, 911–918. Design 4, 891–903.