Journal of Chemical Engineering of Japan, Vol. 45, No. 4, pp.

272–278, 2012 Research Paper

Acoustic Effect on Induction of Cerium Carbonate in Reaction

Crystallization
Xin-Kuai He†, Rayoung Kim, Dongmin Shin and Woo-Sik Kim
Department of Chemical Engineering, ILRI, Kyung Hee University, Yongin 449-701, Korea

Keywords: Ultrasonication, Acoustic Cavitation, Induction, Nucleation, Micromixing, Reaction Crystallization

The influence of ultrasonication and agitation on the induction of nucleation in the reaction crystallization of cerium car-
bonate has been investigated in a semi-batch crystallizer. When the cerium chloride and sodium carbonate reactants are
constantly injected, the induction time depends significantly on ultrasonication and agitation. Due to the acoustic cavi-
tation of ultrasonication promoting micromixing of the reactants, the induction time of cerium carbonate is markedly
reduced. Simultaneously, the acoustic cavitation appears to reduce the energy barrier of nucleation, inducing nucleation
at a lower supersaturation level than with the turbulent fluid motion of agitation. However, the acoustic stream of ultra-
sonication does not promote the induction of nucleation. Meanwhile, agitation also facilitates the induction of nucle-
ation due to turbulent mixing of the reactants. The micromixing resulting from agitation meant the supersaturation in
the solution increases rapidly when increasing the agitation speed, thereby reducing the induction time. The influence of
ultrasonication and agitation on the induction of nucleation has also been compared in terms of the energy dissipation.
With the same energy dissipation, ultrasonication is much more effective than agitation for induction, possibly due to its
unique feature of acoustic cavitation.

induction time. In contrast, using magnesium ions as an ad-

Introduction
Crystallization is a popular industrial operation for the
separation and purification of functional solid products
from organic, inorganic, and polymeric materials. Among
the fundamental phenomena related to crystallization, the
induction of nucleation (induction) is essential and directly
involved in the determination of crystal size, distribution,
and polymorphs. Therefore, extensive studies have already
been conducted over the past several decades to understand
and control induction.
The induction period (induction time) is generally de-
fined as the interval to the first detection of crystals nucleat-
ed from the homogeneous solution, and has been described
in terms of the classical nucleation theory (Sohnel and
Mullin, 1988), allowing the induction time to be predicted
according to the supersaturation. Liu and Nancollas (1973)
also showed that the induction time depends exponential-
ly on the initial solution concentration, and this exponent
varies with the temperature. Furthermore, an intensive in-
vestigation of the factors influencing the induction time
performed by Tai and Chien (2002) using the reaction crys-
tallization of calcium carbonate found that the initial reac-
tant concentration, temperature, solution pH, additives, and
seeds were all influencing factors. Thus, when increasing the
initial reactant concentration, temperature, and pH, the in-
duction time was reduced as the nucleation was promoted.
The amount of seed crystals also contributed to shorten the
Received on August 22, 2011; accepted on December 6, 2011
Correspondence concerning this article should be addressed to W.-S.
Kim (E-mail address: wskim@khu.ac.kr).
†
Current address: School of Packaging and Materials Engineering,
Hunan University of Technology, Zhuzhou 412007, China.
ditive inhibited the nucleation and prolonged the induction
time. Furedi-Milhofer et al. (1993) also demonstrated an
increased induction time when using sodium dodecyl sul-
phate as an additive, and a similar influence of additives was
noted in other studies of metastable zone widths (Myerson
and Jang, 1995; Srinivasan et al., 1999; Rajesh et al., 2000).
Furthermore, the induction time has been studied using
various crystallization systems, such as colloidal (Dixit and
Zukoski, 2002), polymer (Yeh et al., 1979), and gas hydrate
(Kashchiev and Firoozabadi, 2003) crystallization. Also the
model prediction of the induction time was attempted in
cooling crystallization using dynamic equation (Yang et al.,
2007; Kim et al., 2009).
Ultrasonication has long been an area of interest for in-
dustrial technology as it concerns chemical synthesis and
crystallization due to its unique acoustic wave (Cains et al.,
1998; Ruecroft et al., 2005). While the application of ultra-
sonication for chemical synthesis was mainly back in the
early 1950s, the use of ultrasonication for crystallization has
intensified over recent decades. Based on many studies, the
influence of ultrasonication on crystallization is mostly re-
lated to nucleation and induction. In the case of nucleation,
it is promoted by ultrasonication (Ruecroft et al., 2005;
Chaudhari et al., 2008; Kordylla et al., 2009). Thus, when
nucleation is initiated at a lower supersaturation, its rate can
be increased by ultrasonication. Meanwhile, ultrasonication
can significantly reduce the induction time (Lyczko et al.,
2002; Guo et al., 2006; Li et al., 2006; Revalor et al., 2010).
According to Kurotani et al. (2009), the nucleation of amino
acids (l-arginine and l-serine) was inhibited when using
ultrasonication with a low power emission, yet promoted
when increasing the ultrasonic power.

272 Copyright © 2012 Journal

The Society
of Chemical
of Chemical
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Engineers,
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 One explanation of how ultrasonication promotes nucle-
ation is that the acoustic cavitation surmounts the excita-
tion energy barrier associated with nucleation (Ruecroft et
al., 2005). A heterogeneous nucleation mechanism has also
been proposed by Dodds et al. (2007) and Kordylla et al.
(2009), where the acoustic cavitation provides a heteroge-
neous bubble interface for the nucleation, promoting hetero-
geneous nucleation. Furthermore, Kurotani and Hirasawa
(2010) suggested that the nucleation energy barrier is re-
duced by ultrasonication.
Many other studies have also investigated the ultrasonic
effect on crystallization. For example, a stable polymorph
can be directly nucleated by ultrasonication (Higaki et al.,
2001; Louhi-Kultanen et al., 2006; Kurotani and Hirasawa,
2010; Lee et al., 2010), as the acoustic cavitation promotes
the nucleation of stable-phase polymorphs. Crystal ag-
glomeration is also significantly reduced by ultrasonication,
as the acoustic vibration inhibits the aggregation of crys-
tals and re-disperses aggregated crystals (Hyun et al., 2002;
Guo et al., 2007; Kim et al., 2011; Narducci et al., 2011).
Furthermore, ultrasonication can contribute to the produc-
tion of small crystals, as the nucleation rate is promoted to
produce a high number of crystals (Dennehy, 2003; He et al.,
2005; Park and Yeo, 2011).
Accordingly, the present study compares the effects of
ultrasonication and agitation on induction in the reaction
crystallization of cerium carbonate, and explains these ef-
fects using a mechanistic approach based on the classical
nucleation theory. For the experimental measurements, the
crystallization conditions including the agitation, ultrasonic
power, and reactant concentration were all varied in a semi-
batch crystallizer.
1. Experiment
Cerium carbonate was crystallized out based on the reac-
tion of cerium chloride (ACS reagent, Sigma-Aldrich Co.)
and sodium carbonate (ACS reagent, Sigma-Aldrich Co.)
given as Eq. (1),
2CeCl 3 + 3Na 2 CO3 → Ce2 (CO3 )3 + 6NaCl (1)
The cerium chloride and sodium carbonate were dissolved
in purified water and their concentrations monitored
using a conductivity meter (model 1481-60, Cole-Parmer
Instrument Co.). Any solid impurities in the feed solutions
were filtered out by passing the solutions through a micro-
filter (0.1 µm pore diameter) prior to their storage in the
feed tanks.
The crystallizer had a working volume of 1.75 L and was
made of Pyrex glass in the form of a standard Rushton mix-
ing tank. A six-paddle turbine impeller and four baffles were
also installed in the crystallizer for effective mixing of the
reactants fed into the crystallizer. The two feed lines were
separately positioned vertically downward on opposite sides
of the crystallizer, with the tube exits aligned horizontally
at the tip of the impeller. This arrangement of the feed lines
was to minimize local fluctuation of the supersaturation by
Vol. 45 No. 4 2012
preventing any direct contact between the reactants before
being homogeneously dispersed in the crystallizer. An ul-
trasonication device (20 kHz, High Intensity Ultrasonic
Processor, CPX 600, Cole-Parmer Instrument Co.) was also
installed, in which the ultrasonication nozzle thereof was
placed midway between the impeller and the crystallizer
wall, and its tip horizontally was aligned with the impeller.
The crystallizer was initially loaded with purified water
to half its working volume, and the crystallization initiated
by injecting the two reactant solutions into the crystallizer.
The two feed solutions were fed at equal flow rates through
separate tube lines using a Master Flex pump (model 7949-
39, Cole-Parmer Instrument Co.) and their flow rates were
monitored using a floating flow meter (model 3205-30,
Gilmont Instrument Co.). To eliminate any fluctuation in
the feed flow rates, the feed pumps were run at a high speed
and bypass lines were installed to allow fine adjustments of
the flow rates. The reactant feeding was stopped when the
solution reached the full working volume of the crystallizer
(1.75 L). The time period of the reactant feeding for the crys-
tallization was called the feeding time and was always fixed
at 30 min.
The induction of crystallization was visually observed.
Using a background of white paper behind the crystallizer,
a slight colour change of the solution during feeding was
detected and counted as the induction point. Within 1–2 s
after the induction point, the suspension quickly changed
to milky white. Thus, the visual measurement of the induc-
tion time was accurate within 1–2 s of error. To investigate
the influence of the crystallization conditions on induction,
the ultrasonic power was adjusted from 0 to 120 W and the
agitation speed was changed from 200 to 1200 rpm. In addi-
tion, the reactant concentration of cerium chloride was var-
ied from 0.01 to 0.04 mol/L based on the stoichiometry. That
is, according to Eq. (1), the stoichometric reactant concen-
tration of sodium carbonate was 0.015 mol/L for 0.01 mol/L
of cerium chloride. Thus, the variation of sodium carbonate
stoichiometrically ranged from 0.015 to 0.06 mol/L for 0.01
to 0.04 mol/L of cerium chloride. The temperature of the
crystallization was always controlled at 25.0 1.0°C (Figure
1).
2. Results and Discussion
Ultrasonication was applied to modify the induction of
the nucleation of cerium carbonate in reaction crystalliza-
tion. Without ultrasonication, the induction of the nucle-
ation depended on the agitation speed, as shown in Figure
2. Thus, the induction time of 36 s at 500 rpm dropped
somewhat to 31 s at 1200 rpm. This was due to micromix-
ing of the turbulent flow by the agitation, which mixed the
reactant on a molecular level to produce cerium carbonate.
Therefore, the supersaturation level in the solution increased
rapidly over a certain level for the primary nucleation, and
the increment of the supersaturation became faster when
increasing the agitation speed. This was consistent with the
fact that the apparent kinetics of a fast reaction are pre-
273

Fig. 1 Schematic diagram of experimental apparatus: (a) 1. agita-
tor, 2. impeller, 3. crystallizer, 4. ultrasonic device, 5. 3-way
valves, 6. pumps, 7. by-pass way, 8. flow meters, and 9. electron
microscope, and (b) design of standard Rushton crystallizer:
DT =H=12.8 cm, DA =E=4.3 cm, Q=0.5 cm, U=0.1 cm,
J=1.1 cm, L=1.1 cm, W=0.9 cm, and Z=0.8 cm. Working
volume=1.75 L
dominantly determined by the micromixing time depending
on the intensity of the turbulence (Kim and Tarbell, 1996).
Furthermore, it also agrees with the observation in reaction
crystallization that turbulent agitation enhances the actual
nucleation rate (Kim et al., 2004). However, when adding
ultrasonication to the agitation, the induction was signifi-
cantly promoted, dropping below 20 s, even with a low ultra-
sonic power of 6 W.
More details of the influence of the ultrasonic power on
the induction are presented in Figure 3. Even a low ultra-
sonic power of 6 W significantly promoted the induction
(19 s), even making it much shorter than the influence of
only a high agitation speed of 1200 rpm (31 s). This was
due to the acoustic effect of the ultrasonication. That is, ul-
trasonication is an acoustic wave with a periodic cycle of
compression (high pressure) and rarefaction (low pressure).
When the rarefaction is strong enough to exceed the molec-
ular interaction of the medium, the acoustic wave generates
micro bubbles, known as acoustic cavitation. These micro
bubbles then collapse in the successive compression cycle,
274
Fig. 2 Influence of agitation on induction time of cerium carbonate
crystallization
Fig. 3 Influence of ultrasonication on induction time of cerium car-
bonate crystallization
producing a high energy with chemical and mechanical ef-
fects. According to Monnier et al. (1999), ultrasonication is
highly effective for micromixing for a fast reaction. Here,
the micromixing time was drastically reduced to 0.005 s,
which is only theoretically achievable at a very high agita-
tion speed (Re=100,000) in the mixing tank, the equivalent
of an agitation speed of 3200 rpm for the present system.
In addition, a high acoustic energy can help overcome the
nucleation energy barrier, allowing induction to occur at a
low supersaturation level (Ruecroft et al., 2005). Therefore,
the ultrasonication had a greater effect than the turbulent
agitation on promoting the nucleation of cerium carbonate
in the reaction crystallization.
In addition, at an agitation speed below 500 rpm, a fur-
ther increase in the ultrasonic power slightly reduced the
induction time. As a result, the induction occurred at 15 s
with a high ultrasonic power of 90 W. However, with an agi-
tation speed above 900 rpm, the induction time appeared
almost insensitive to an ultrasonic power above 6 W, which
was due to the macromixing effect of the agitation on the
induction. In addition to acoustic cavitation, ultrasonica-
tion also generates an acoustic stream, a fluid motion driven
Journal of Chemical Engineering of Japan
by the absorption of high-amplitude acoustic oscillations.
However, in the present case, this oscillatory fluid motion
was not strong enough for homogenous macromixing of the
reactants. Thus, when using ultrasonication without agita-
tion, the acoustic wave was irregularly effective for the in-
duction of cerium carbonate. Consequently, the nucleation
of cerium carbonate occurred locally due to a non-homo-
geneous high supersaturation, and the induction time was
irreproducible even with a high ultrasonic power of 120 W.
As has been mentioned previously by Ruecroft et al. (2005)
and Lakerveld et al. (2011), the intensive field transferred by
ultrasonication was around 2–5 cm from the probe, thereby
limiting the application of ultrasonication on a large scale.
Therefore, in the present experiment, a minimum agita-
tion of 200 rpm was required for consistent reproduction
of the induction of cerium carbonate. When increasing the
agitation, the macromixing of the reactants was improved
to homogenize the ultrasonication effect on the micromix-
ing of the reactants and nucleation of cerium carbonate in
the crystallizer. A similar observation was also reported by
Kim et al. (2011), where a minimum agitation of 200 rpm
was necessary for the homogeneous suspension of crystals
in reaction crystallization.
The fluid motion of micromixing is frequently described
in terms of energy dissipation, and it has already been re-
ported that an acoustic wave is much more effective for
energy dissipation than impeller agitation (Ngyuen et al.,
2010). In the present study, an ultrasonic power (electric
power) of 6 W dissipated an energy of 1.884 W/kg into the
medium, which was equivalent to the energy dissipation of
impeller agitation at 840 rpm. Thus, the induction time was
less sensitive to an ultrasonic power above 6 W than to the
agitation, due to the highly effective and unique energy dis-
sipation mechanism of ultrasonication. The effects of the
impeller agitation and ultrasonication on the induction in
terms of the energy dissipation will be discussed later in
detail.
Figure 4 presents the influence of the reactant concen-
tration in relation to various agitation and ultrasonication
conditions. When increasing the reactant concentration,
the supersaturation level in the solution increased rapidly,
resulting in a reduction in the induction time. However,
the influence of agitation and ultrasonication on induction Fig. 4 The influence of reactant concentration on induction time lev-
also appeared clearly when varying the reactant concentra- el at the induction point of cerium carbonate crystallization:
tion. Due to poor macromixing at a low agitation speed of (a) agitation speed varied from 500 to 1200 rpm, with ultra-
500 rpm, the induction time was high and varied signifi- sonication fixed at 6 W, (b) agitation speed varied from 500 to
cantly with the reactant concentration, as shown in Figure 1200 rpm, with ultrasonication fixed at 30 W, and (c) agitation
speed varied from 500 to 1200 rpm, with ultrasonication fixed
4(a). Yet, this dependency of the induction time on the reac-
at 60 W
tion concentration was greatly attenuated when increasing
the agitation speed. In the case of high ultrasonic powers
of 30 and 60 W (Figures 4(b) and (c)), the induction time The influence of the agitation and ultrasonication on the
profile according to the reactant concentration was also very induction was compared in terms of the energy dissipation
similar to the above. Here, it should be noted that ultra- (ε), which is frequently used for the quantitative description
sonication was quite effective for induction, as the induction of a turbulent fluid motion and the micromixing intensity.
time profile according to the reactant concentration was less The energy dissipation in the Rushton mixing tank crystal-
dependent on the ultrasonication power than on the agita- lizer caused by the agitation was calculated using the Power
tion speed. consumption (PC) as (McCabe et al., 2001) given by Eq. (2).

Vol. 45 No. 4 2012 275

 N P nr3 Da6 ρ
PC = (2)
gc
Here, nr was the rotational speed of the impeller per second,
Da was the diameter of the impeller, and ρ was the density
of the solution. NP indicating the power number depended
on the mixing Reynolds number, defined as nrDa2ρ/μ, where
was the viscosity. Above a mixing Reynolds number of 5000,
the power number remained constant at 6.0 for the Rushton
mixing tank. The energy dissipation by the agitation was
then calculated using Eq. (3).
PC
ε= (3)
ρV
Here, V was the volume of the solution (1.75 L). Meanwhile,
Fig. 5 Comparison of induction time influenced by agitation and ul-
the energy dissipation by the ultrasonication was estimat- trasonication in terms of energy dissipation; reactant concen-
ed from the experimental measurement of Monnier et al. tration of cerium chloride fixed at 0.003 M
(1999), where the linearity between the electric power of the
ultrasonication and the power dissipated to the solution by
the ultrasonication was found to be Pdiss =0.54Pelec. This cor-
relation agreed well with the current results for the range of
ultrasonication power from 0 to 150 W and solution volume
from 0.1 to 3.75 L. The energy dissipation by the ultrasonica-
tion was then estimated as Eq. (4)
Pdiss
ε= (4)
ρV

Using Eqs. (3) and (4), the influence of the agitation and
ultrasonication on the induction was compared, as shown
in Figure 5. Here, when investigating the influence of the
agitation on the induction, no ultrasonication was applied.
However, when checking the influence of the ultrasonica-
tion, gentle agitation at 200 rpm was applied to ensure
a consistent and reproducible induction time. The energy
dissipation by the agitation at 200 rpm was negligible when
compared to the energy dissipation by the lowest ultrason-
ication power of 6 W. The reactant concentration (cerium
chloride) was fixed at 0.03 M. As shown in Figure 5, ultra-
sonication achieved a higher energy dissipation than agi-
tation, implying that ultrasonication is more effective than
agitation for micromixing the reactants. Even with the
same energy dissipation, ultrasonication induced nucle-
ation much faster than agitation, possibly due to the unique
acoustic cavitation caused by ultrasonication, which pro-
motes both micromixing of the reactants and nucleation of
the product.
The effectiveness of ultrasonication over agitation for
induction was investigated using the classical nucleation
theory, as shown in Figure 6. According to the nucleation
theory, the induction time (ti) is inversely proportional to
the nucleation rate, and then simply expressed as Eq. (5).
 ΔG* 
t i  exp   (5)
 kT 
Here, ΔG* is the energy barrier for nucleation, depending
on the supersaturation as ∼(1/ln2 S), k is the Boltzmann
constant, and T is the absolute temperature. The induction
Fig. 6 The predictions of induction time influenced by agitation and
ultrasonication by Volmer’s nucleation model; reactant con-
centration of cerium chloride fixed at 0.003 M
time can then be expressed as a function of the supersatura-
tion (S) as Eq. (6).
 α 
t i  exp  2  (6)
 ln S 
The supersaturation levels at the induction points in Figure
5 were calculated under the assumption of complete conver-
sion of the reactants in the crystallizer, and then plotted in
the log–log graph in Figure 6. Furthermore, the solubility
of the cerium carbonate crystals was experimentally mea-
sured as 1.65×10−5 using EDTA titration. As predicted in
Eq. (6), the plots showed good linearity, yet different slopes
(α), indicating different energy barriers for nucleation. That
is, the nucleation energy barrier appeared lower with ultra-
sonication than with agitation. According to Dodds et al.
(2007) and Kordylla et al. (2009), the ultrasonic effect can
be mathematically described in terms of a heterogeneous
nucleation mechanism, where the cavitation bubbles provide
a foreign surface to promote nucleation. Thus, the induction
occurred at a much lower supersaturation with ultrasonica-

276 Journal of Chemical Engineering of Japan

tion than with agitation. A similar result was observed by
Kurotani and Hirasawa (2010) in the phase transformation
of sulfamerazine and also attributed to a reduction in the
nucleation energy barrier, resulting in a shorter induction
time at a lower supersaturation level.
Conclusions
The induction of cerium carbonate nucleation in reac-
tion crystallization was found to depend on both agitation
and ultrasonication due to their micro- and macromixing
effects on the reactants. The bulky fluid motion for macro-
mixing and random turbulent eddies for micromixing were
driven by agitation. Thus, the induction time was reduced
when increasing the agitation speed. Meanwhile, the acous-
tic wave of ultrasonication generated acoustic cavitation and
an acoustic stream. The high acoustic impact of the acoustic
cavitation, including mechanical and thermal energy, was
highly effective for the induction of nucleation. Thus, the
induction time was significantly reduced by even a low ul-
trasonication power of 6 W. However, the acoustic stream
from the turbulent motion of the fluid was not rigorous
enough, even for homogeneous bulky motion of the reac-
tants. Therefore, when comparing their influence on induc-
tion in terms of energy dissipation, ultrasonication promot-
ed induction much more than agitation, as ultrasonication
reduced the energy barrier of nucleation.
Acknowledgements
The authors would like to thank Kyung Hee University for their fi-
nancial support (KHU-20110253).
Literature Cited
Cains, P. W., P. D. Martin and C. J. Price; “The Use of Ultrasound in
Industrial Chemical Synthesis and Crystallization. 1. Application
to Synthetic Chemistry,” Org. Process Res. Dev., 2, 34–48 (1998)
Chaudhari, P., P. Uttekar, N. Waria and A. Ajb; “Study of Different
Crystal Habits Formed by Recrystallization Process and Study
Effect of Variables,” Res. J. Pharm Technol., 1, 381–385 (2008)
Dennehy, R. D.; “Particle Engineering Using Power Ultrasound,” Org.
Process Res. Dev., 7, 1002–1006 (2003)
Dixit, N. M. and C. F. Zukoski; “Nucleation Rates and Induction Times
during Colloidal Crystallization: Links between Models and
Experiments,” Phys. Rev. E, 66, 05 1602-1-10 (2002)
Dodds, J., F. Espitalier, O. Louisnard, R. Grossier, R. David, M. Hassoun,
F. Bailon, C. Gatumel and N. Lyczko; “The Effect of Ultrasound on
Crystallization-Precipitation Processes: Some Examples and a New
Segregation Model,” Part. Part. Syst. Char., 24, 18–28 (2007)
Füredi-Milhofer, H., R. Bloch, D. Skrtic, N. Filipovic-Vincekovic and
N. Garti; “Induction of Crystallization of Specific Calcium Oxalate
Hydrate in Micellar Solution of Surfactants,” J. Dispersion Sci.
Technol., 14, 355–371 (1993)
Guo, Z., A. G. Jones and N. Li; “The Effect of Ultrasound on
the Homogeneous Nucleation of BaSO4 during Reaction
Crystallization,” Chem. Eng. Sci., 61, 1617–1626 (2006)
Guo, Z., A. G. Jones, N. Li and S. Germana; “High Speed Observation
of the Effect of Ultrasound on Liquid Mixing and Agglomerated
Crystal Breakage Process,” Powder Technol., 171, 146–153 (2007)
Vol. 45 No. 4 2012
He, M., E. Forssberg, Y. Wang and Y. Han; “Ultrasonication-Assisted
Synthesis of Calcium Carbonate Nanoparticles,” Chem. Eng.
Commun., 192, 1468–1481 (2005)
Higaki, K., S. Ueno, T. Koyano and K. Sato; “Effects of Ultrasonic
Irradiation on Crystallization Behavior of Tripalmitoylglycerol and
Cocoa Butter,” J. Am. Oil Chem. Soc., 78, 513–518 (2001)
Hyun, J. K., J. S. Kim, S. D. Kim, H. S. Yoon, J. Y. Lee and W.-S. Kim;
“Ultrasonic Study on Conglomeration of Cerium Oxalate Particles
Produced by Reaction Crystallization in Series Reactor Including
T-Mixer and Stirred Tank,” J. Chem. Eng. Japan, 35, 1211–1218
(2002)
Kashchiev, D. and A. Firoozabadi; “Induction Time in Crystallization of
Gas Hydrates,” J. Cryst. Growth, 250, 499–515 (2003)
Kim, D. Y., M. Paul, J.-U. Repke, G. Wozny and D. R. Yang; “Modeling
of Crystallization Process and Optimization of the Cooling
Strategy,” Korean J. Chem. Eng., 26, 1220–1225 (2009)
Kim, J. M., S. M. Chang, K. S. Kim, M. K. Chung and W.-S. Kim;
“Acoustic Influence on Aggregation and Agglomeration of
Crystals in Reaction Crystallization of Cerium Carbonate,”
Colloids Surf. A, 375, 193–199 (2011)
Kim, W.-S. and J. M. Tarbell; “Micromixing Effects on Barium Sulfate
Precipitation in an MSMPR Reactor,” Chem. Eng. Commun., 146,
33–48 (1996)
Kim, W. S., K.-S. Kim, J.-S. Kim, M. D. Ward and W.-S. Kim; “Crystal
Agglomeration of Europium Oxalate in Reaction Crystallization
Using Double-Jet Semi-Batch Reactor,” Mater. Res. Bull., 39, 283–
296 (2004)
Kordylla, A., T. Krawczyk, F. Tumakaka and G. Schembecker;
“Modeling Ultrasound-Induced Nucleation during Cooling
Crystallization,” Chem. Eng. Sci., 64, 1635–1642 (2009)
Kurotani, M. and I. Hirasawa; “Effect of Ultrasonic Irradiation on the
Selective Polymorph Control in Sulfamerazine,” Chem. Eng. Res.
Des., 88, 1272–1278 (2010)
Kurotani, M., E. Miyasaka, S. Ebihara and I. Hirasawa; “Effect of
Ultrasonic Irradiation on the Behavior of Primary Nucleation of
Amino Acids in Supersaturated Solution,” J. Cryst. Growth, 311,
2714–2721 (2009)
Lakerveld, R., N. G. Verzijden, H. Kramer, P. Jansens and J. Grievink;
“Application of Ultrasound for Start-Up of Evaporation Batch
Crystallization of Ammonium Sulfate in a 75-L Crystallizer,”
AIChE J., 57, 3367–3377 (2011)
Lee, Y. L., R. I. Ristic, L. L. DeMatos and C. M. Martin; “Crystallisation
Pathways of Polymorphic Triacylglycerols Induced by Mechanical
Energy,” J. Phys. Conf. Ser., 247, 1–16 (2010)
Li, H., H. Li, Z. Guo and Y. Liu; “The Application of Power Ultrasound
to Reaction Crystallization,” Ultrason. Sonochem., 13, 359–363
(2006)
Liu, S. T. and G. H. Nancollas; “Linear Crystallization and Induction-
Period Studies of the Growth of Calcium Sulphate Dihydrate
Crystals,” Talanta, 20, 211–216 (1973)
Louhi-Kultanen, M., M. Karjalainen, J. Rantanen, M. Huhtanen and J.
Kallas; “Crystallization of Glycine with Ultrasound,” Int. J. Pharm.,
320, 23–29 (2006)
Lyczko, N., F. Espitalier, O. Louisnard and J. Schwartzentruber; “Effect
of Ultrasound on the Induction Time and the Metastable Zone
Width of Potassium Sulphate,” Chem. Eng. J., 86, 233–241 (2002)
McCabe, W. L., J. C. Smith and P. Harriott; Unit Operations of
Chemical Engineering, 6th ed., p. 207 McGraw Hill, Boston, U.S.A.
(2001)
Monnier, H., A. M. Wilhelm and H. Delmas; “The Influence of
Ultrasound on Micromixing in a Semi-Batch Reactor,” Chem. Eng.
Sci., 54, 2953–2961 (1999)
277
Myerson, A. and A. M. Jang; “A Comparison of Binding Energy and
Metastable Zone Width for Adipic Acid with Various Additives,” J.
Cryst. Growth, 156, 459–466 (1995)
Narducci, O., A. G. Jones and E. Kougoulos; “Continuous
Crystallization of Adipic Acid with Ultrasound,” Chem. Eng. Sci.,
66, 1069–1076 (2011)
Nguyen, A.-T., J.-M. Kim, S.-M. Chang and W.-S. Kim; “Taylor Vortex
Effect on Phase Transformation of Guanosine 5-Monophosphate
in Drowning-out Crystallization,” Ind. Eng. Chem. Res., 49, 4865–
4872 (2010)
Park, S.-J. and S.-D. Yeo; “Liquid Antisolvent Recrystallization of
Phenylbutazone and the Effect of Process Parameters,” Sep. Sci.
Technol., 46, 1273–1279 (2011)
Rajesh, N. P., K. Meera, K. Srinivasan, P. S. Raghavan and P. Ramasamy;
“Effect of EDTA on the Metastable Zone Width of ADP,” J. Cryst.
Growth, 213, 389–394 (2000)
Revalor, E., Z. Hammadi, J.-P. Astier, R. Grossier, E. Garcia, C. Hoff, K.
Furuta, T. Okustu, R. Morin and S. Veesler; “Usual and Unusual
Crystallization for Solution,” J. Cryst. Growth, 312, 939–946 (2010)
278
Ruecroft, G., D. Hipkiss, T. Ly, N. Maxted and P. W. Cains;
“Sonocrystallization: The Use of Ultrasound for Improved
Industrial Crystallization,” Org. Process Res. Dev., 9, 923–932
(2005)
Sohnel, O. and J. W. Mullin; “Interpretation of Crystallization Induction
Periods,” J. Colloid Interface Sci., 123, 43–50 (1988)
Srinivasan, K., K. Meera and P. Ramasamy; “Enhancement of
Metastable Zone Width for Solution Growth of Potassium Acid
Phthalate,” J. Cryst. Growth, 205, 457–459 (1999)
Tai, C. and W.-C. Chien; “Effects of Operating Variables on the
Induction Period of CaCl2-NaCO3 System,” J. Cryst. Growth, 237-
239, 2142–2147 (2002)
Yang, D. R., K. S. Lee, J. S. Lee, S. G. Kim, D. H. Kim and Y. K. Bang;
“Modeling of Metastable Zone Width Behavior with Dynamic
Equation,” Ind. Eng. Chem. Res., 46, 8185–8165 (2007)
Yeh, G. S. Y., K. Z. Hong and D. L. Krueger; “Strain-Induced
Crystallization, Part IV: Induction Time Analysis,” Polym. Eng.
Sci., 19, 401–405 (1979)
Journal of Chemical Engineering of Japan