Journal of Crystal Growth 212 (2000) 489}499

Estimation of crystal growth kinetics using di!erential

scanning calorimetry
Rajeev Mohan, Kenneth A. Boateng, Allan S. Myerson*
Department of Chemical Engineering, Polytechnic University, Six MetroTech Center, Brooklyn, NY 11201, USA
Received 2 February 1999; accepted 19 January 2000
Communicated by R.W. Rousseau
Abstract
Seeded isothermal growth experiments are performed in a di!erential scanning calorimeter (DSC) and growth kinetics
are obtained from the desupersaturation curve. Experiments are performed at temperatures ranging from 0 to 2003C and
high pressures utilizing sealed DSC pans. The technique introduced in this paper is useful in estimating growth kinetics in
a relatively short period of time and under conditions of high pressure and temperature or, when only small amounts of
material are available. Results obtained employing this method are in reasonable agreement with those in the
literature. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Growth kinetics; Di!erential scanning calorimeter; DSC; Desupersaturation curve; Seeded isothermal; Crystallization
1. Introduction and background
Crystallization from solution can be thought of
as a two-step process. The "rst step is the phase
separation or &birth' of a new crystal } nucleation.
The second step is the subsequent addition of mass
of these crystals } crystal growth. Knowledge of the
kinetics of these phenomena is crucial in the devel-
opment, analysis and control of crystallization pro-
cesses. This has led to many kinetic studies in Refs.
[1}3], a number of experimental techniques [3}6],
and a number of methods of measuring growth
kinetic parameters [7}10].
*Corresponding author. Current address: Illinois Institute of
Technology, 103 Siegal Hall, South Dearborn St., Chicago, IL
60616, USA. Tel.: #1-312-567-3163; fax: #1-312-567-5205.
E-mail address: myerson@iit.edu (A.S. Myerson).
There are a number of methods used to measure
crystal growth rates. These include methods involv-
ing growth of single crystals at constant super-
saturations, methods involving suspension of seed
crystals, and most commonly the mixed suspen-
sion, mixed product removal (MSMPR) continu-
ous crystallizer operating at a steady state. The
population balance concepts along with measured
crystal size distributions are used for obtaining the
growth kinetics. All these measurement techniques,
also known as direct methods, are time consuming
and require a signi"cant number of experiments at
several di!erent supersaturations for each temper-
ature of interest to obtain the kinetic parameters.
The indirect methods [9}12] are based on the
measurement of the solution concentration versus
time in seeded isothermal batch experiments. This
is called the &desupersaturation curve' since
the concentration and solubility can be used to
0022-0248/00/$- see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 0 ) 0 0 3 0 9 - 2
Nomenclature
supersaturation C/C*
density of the solution (g/cm`)
A Arrhenius constant
A
''
total surface area per 100 g of solvent (cm`/100 g solvent)
CH concentration at saturated conditions (g solute/100g solvent)
C concentration di!erence (g solute/100g solvent)
CQ , C$ "rst and second derivatives of concentration di!erence from desupersaturation
d average diameter of a crystal solute before addition of solvent (cm)
d

average diameter of the undissolved solute particle after addition of solvent (cm)
E
'
activation energy (kJ g/mol)
F overall shape factor
g growth order
k

linear growth rate coe$cient [(m/s (kg solute/kg solvent)); m/s; cm/s]
K

mass growth rate coe$cient [(g/cm`/s (kg solute/kg solvent)); g/cm`; kg/m`/s]

"
average seed size, cm
N number of crystal particles
R universal gas constant (kJ g/mol 3C)
R
'
mass rate of crystal growth [g/cm`/s; kg/m`/s; cm/s; m/s]
SA surface area per unit mass of solute (cm`/g)
t time (s or min)
temperature (3C)
v

average volume of a crystal particle (cm`)

<

average volume of the undissolved solute particle after addition of solvent (cm`)
Subscripts
TO total
Superscripts
and G "rst and second derivatives with respect to time
H saturated condition
calculate the supersaturation of the system versus
time. The batch methods are faster and easier ex-
perimentally. A variety of techniques can be used to
measure the desupersaturation curve, such as
measurement of concentration, density or through
light scattering experiments [12]. In cases where
crystal growth kinetics are needed at high temper-
ature and greater than atmospheric pressure the
indirect methods become di$cult and special
equipment must be designed.
In this study, a di!erential scanning calorimeter
with a sealed high-pressure sample pan is used
to obtain the desupersaturation curve from the
measurement of enthalpy of crystallization. The
DSC has the advantage of being automated and
allowing kinetic measurement on microsamples at
extreme conditions of pressure and temperature.
The sample pan used in this study has the capacity
to withstand pressures up to 24 atm and temper-
atures up to 3003C. This approach is one of the
many thermal methods based on the measurements
of dynamic relationship between temperature and
enthalpy/heat. The purpose of this study is to pres-
ent a simple and fast method for estimation of
crystal growth kinetics with microsamples using
a seeded isothermal experiment in a DSC pan.
490 R. Mohan et al. / Journal of Crystal Growth 212 (2000) 489}499
Myerson and Jang [13] have used the DSC experi-
ment to obtain the metastable zone width for adipic
acid with various additives.
2. Theory
A number of models are available to estimate the
growth kinetics from the desupersaturation curve
and are summarized by Tavare [14]. In the present
study, the simplest of the methods, the initial deriv-
ative model [10] has been employed. This method
uses the derivatives of the desupersaturation curve
at time zero. The model conditions are taken to be
isothermal, and concentration change is assumed
to be due to crystal growth and not nucleation. The
growth is considered to be size independent [15]
while growth rate dispersion is assumed to be negli-
gible.
The main equations to obtain the growth kinet-
ics from the initial derivative model [10] are pre-
sented in this section. The expression for the
relationship between supersaturation and crystal
growth in terms of mass #ux is
R
'
"K

C"
1
A
''
d`
"
dt
F. (1)
The power g (growth order) and the constant
K

(mass growth rate coe$cient) of Eq. (1) can be

obtained from the relations
g"
2FC
"
3
"
A
''
#
C
"
C$
"
CQ `
"
(2)
and
K

"!
CQ
"
A
''
C
"
. (3)
The linear growth rate coe$cient k

can then be
calculated from K

with the following equation:

k

"K

F
3
. (4)
The derivatives CQ
"
and C$
"
are usually ob-
tained by "tting the desupersaturation curve to
a second-order polynomial of the form,
C"a
"
#a

t#a
`
t`. (5)
Di!erentiating with respect to time, and equating
time to zero we obtain,
C
"
"a
"
, CQ
"
"a

, and C$
"
"2a
`
. (6)
The mass growth rate coe$cient is temperature
dependent, and its temperature dependence con-
forms to the Arrhenius equation,
lnK

"lnA!
E
'
R
1

. (7)
The activation energy E
'
can be calculated from
the slope of a plot of ln K

versus 1/. The activa-

tion energy determines whether the rate-controlling
step for the growth process is di!usion or surface
integration [3,16].
3. Experimental procedure
A Perkin-Elmer DSC 7 thermal analyzer is used
for this study. The DSC experiments are carried out
in an inert nitrogen atmosphere with a purge rate of
40 ml/min. The experimental temperature ranged
from 0 to 1923C, depending on the melting point of
the material and the availability of solubility data.
Solute crystals are initially sieved and one size
fraction chosen for further study. The initial aver-
age crystal size for each solute is therefore known.
This average size is used in all the calculations for
individual solutes. The Perkin-Elmer O-ring, stain-
less-steel, large volume capsules (LVC) are used as
DSC sample pans. The LVC, as mentioned earlier,
is capable of withstanding internal pressures due to
high temperatures and also suppresses the vapor-
ization of solvents. A small amount of solute is
weighed in a sample pan. The solvent is then added
to this pan with the help of a micropipette. The
mass of the solute and solvent added are predeter-
mined so as to allow for a saturated solution with
the seeds to exist at the desired measuring temper-
ature. For example, if an experiment needs to be
conducted at 803C the mass of solute and solvent
added must be su$cient to make a saturated solu-
tion at 85}873C.
Fig. 1 is a schematic diagram showing the com-
ponents of a typical di!erential scanning calori-
meter. Weighed quantities of sample and reference
R. Mohan et al. / Journal of Crystal Growth 212 (2000) 489}499 491
Fig. 1. Schematic diagram of a DSC.
material are held in the small pans labeled S and R.
The thermocouple on the right (labeled control TC)
controls the rate at which the furnace must be
heated or cooled. In the DSC, the sample and
reference are continuously subjected to heating or
a cooling cycle. As a result heat is added or re-
moved as required by the system to maintain both
the pans at identical temperatures. The heat added
or removed is recorded and gives a measure of heat
lost or gained as a consequence of phase changes
occurring in the sample with the progress of time.
In this study, we are interested in the phase change
that occurs during crystallization.
The sample is "rst heated to about 2}33C below
the saturation temperature of the solution in the
pan at a rate of 403C/min. This ensures that the
solution is saturated and seed crystals are present
(which are formed from the undissolved solute).
The sample is then maintained at this temperature
for about 20}60 min to bring the system to equilib-
rium. The equilibrium state is achieved when the
#uctuation in the heat #ow curve from the DSC is
negligible. The time to achieve this equilibrium
varies for di!erent systems. The sample is then
cooled rapidly (about 2}33C), at a rate of 1803C/
min (system maximum), to reach the temperature
(isothermal temperature) at which the growth kin-
etic data is required. The time for temperature drop
is negligible due to the high cooling rates adopted
and it is assumed that there is no growth during
this time period. The solution is then maintained at
this isothermal temperature for about 30}60 min
while the seed crystals grow. The heat liberated
during the growth process is utilized in obtaining
the desupersaturation curve.
The mass, size and surface area is calculated from
the solubility data assuming a monodisperse initial
crystal size distribution and assuming that all crys-
tals dissolve equally at the same rate. It is also
assumed that the seed crystal growth is uniform
and there is no loss of the initial seed shape. The
calculations are summarized below. The average
volume (assuming sphere) of a crystal particle at
room temperature is given by
v

"
4
3

d
2
`
. (8)
The number of particles N in the sample pan is then
calculated by
N"
total mass of the solute in the pan
mass of a single-crystal particle
. (9)
492 R. Mohan et al. / Journal of Crystal Growth 212 (2000) 489}499
Fig. 2. A sample trace from DSC.
Fig. 3. Desupersaturation curve: adipic acid in ethanol.
The number of particles N is assumed to remain
constant throughout the experiment. The average
volume of the single seed (undissolved solute) at the
start of the experiment is given by
<

"
total mass of seeds at the start
N
. (10)
Average diameter of the undissolved particle at
the start of the experiment is given by
d

"

<

`
. (11)
The surface area per unit mass SA and the total
surface area A
''
of the undissolved particle/100g
solvent is given by
SA"
total surface area of undissolved solute
total mass of undissolved solute
(12)
and
A
''
"SA(mass of undissolved solute/
100 g solvent). (13)
The growth kinetics is calculated from the Eqs.
(1)}(5). A sample heat #ow-time curve is shown in
Fig. 2. The growth kinetics for the experiment cor-
responding to the heat #ow-time curve in Fig. 2 is
outlined below.
4. Sample calculation
Adipic acid in ethanol solution has been chosen
for the sample DSC calculation. The amount of
adipic acid added is su$cient to saturate the
solution at 583C. The sample is "rst heated to 533C
at a rate of 403C/min. The sample is then main-
tained at this temperature for about 20 min to bring
the system to equilibrium. The sample is then
cooled rapidly to 503C, at a rate of 1803C/min. The
solution is then maintained at this isothermal tem-
perature for about 30 min while the seed crystals
grow. The heat liberated during the growth process
is utilized in obtaining the desupersaturation curve
as shown in Fig. 3.
Amount of adipic acid"0.0101g, amount of
ethanol in sample"0.0289g, solubility equation
for adipic acid in ethanol is given by,
ln S"0.0354*(3C)#1.5481,
where S is g solute/100 g ethanol.
Amount of solute that crystallizes on cooling
from 53 to 503C is 3.093 g/100 g of ethanol. Amount
of solute that crystallizes per 0.0289 g ethanol is
0.00089g.
The data obtained from DSC is converted to
obtain the desupersaturation curve as outlined in
Table 1. The desupersaturation curve is shown in
Fig. 3. The average diameter of adipic acid used,
d"0.00889 cm, the density of adipic acid, "
1.36g/cm`.
R. Mohan et al. / Journal of Crystal Growth 212 (2000) 489}499 493
Table 1
Calculation sample DSC trace
Actual DSC data
Time H Time Heat #ow Solid crystallized c}c*
(min) (mW) (min)
(J/g) (J) (g) g/100 g
solvent
g/100 g
solvent
20.75 18.36307 0.0000 0.0000 0.0000 0.0000 0.0000 3.0933
20.8 15.95603 0.0500 0.0915 0.0036 0.0000 0.0349 3.0584
20.85 6.643227 0.1000 0.6317 0.0246 0.0001 0.2413 2.8520
20.9 3.213722 0.1500 1.6599 0.0647 0.0002 0.6340 2.4593
20.95 3.154773 0.2000 2.8202 0.1099 0.0003 1.0771 2.0162
21 4.74669 0.2500 3.9191 0.1528 0.0004 1.4968 1.5965
21.05 6.984725 0.3000 4.8684 0.1898 0.0005 1.8593 1.2340
21.1 9.23757 0.3500 5.6425 0.2199 0.0006 2.1550 0.9383
21.15 11.22413 0.4000 6.2513 0.2437 0.0007 2.3875 0.7058
21.2 12.85002 0.4500 6.7188 0.2619 0.0007 2.5660 0.5273
21.25 14.12106 0.5000 7.0725 0.2757 0.0008 2.7011 0.3922
21.3 15.08777 0.5500 7.3378 0.2860 0.0008 2.8025 0.2908
21.35 15.80996 0.6000 7.5358 0.2937 0.0008 2.8781 0.2152
21.4 16.34777 0.6500 7.6831 0.2995 0.0008 2.9343 0.1590
21.45 16.73718 0.7000 7.7924 0.3037 0.0009 2.9761 0.1172
21.5 17.0145 0.7500 7.8738 0.3069 0.0009 3.0072 0.0861
21.55 17.20964 0.8000 7.9347 0.3093 0.0009 3.0304 0.0629
21.6 17.34613 0.8500 7.9805 0.3111 0.0009 3.0479 0.0454
21.65 17.43963 0.9000 8.0153 0.3124 0.0009 3.0612 0.0321
21.7 17.50497 0.9500 8.0416 0.3135 0.0009 3.0713 0.0220
21.75 17.54911 1.0000 8.0614 0.3142 0.0009 3.0788 0.0145
21.8 17.57844 1.0500 8.0762 0.3148 0.0009 3.0845 0.0088
21.85 17.59702 1.1000 8.0868 0.3152 0.0009 3.0885 0.0048
21.9 17.60922 1.1500 8.0939 0.3155 0.0009 3.0912 0.0021
21.95 17.61706 1.2000 8.0980 0.3157 0.0009 3.0928 0.0005
22 17.62172 1.2500 8.0993 0.3157 0.0009 3.0933 0.0000
The average volume of a crystal particle at room
temperature is given by
v

"
4
3

d
2
`
"3.68E-7 cm`.
The number of particles N in the sample pan is then
calculated by
N"
total mass of the solute in the pan
mass of a single-crystal particle
"20 147.
The average volume of the single seed (undis-
solved solute) at the start of the experiment is
given by
<

"
total mass of seeds at the start
N
"4.41E-8cm`.
Average diameter of the undissolved particle at the
start of the experiment is given by
d

"

<

`
"0.004382cm.
The surface area per unit mass SA and the total
surface area A
''
of the undissolved particle/100g
494 R. Mohan et al. / Journal of Crystal Growth 212 (2000) 489}499
solvent is given by
SA"
total surface area of undissolved solute
total mass of undissolved solute
"1006.84 cm`/g undissolved solute
and
A
''
"SA(mass of undissolved solute/
100 g solvent)"4205.05 cm`/100 g solvent.
The coe$cients of the second-degree polynomial "t
of the desupersaturation curve in Fig. 3 are
C"3.0933!7.3009t#4.2988t`.
It is to be noted that there is an obvious di!er-
ence in the slope at t"0 between data and "t. This
trend has been observed in several other experi-
ments and also in isothermal di!erent seeded
growth experiments using volumes above 500 ml.
Di!erentiating the above equation with respect
to time and equating time to zero we obtain
C
"
"3.0933 g/100 g solvent,
CQ
"
"!7.3009 g/100 g solvent/min,
C$
"
"8.7416 g/100 g solvent/min.
The power g (growth order) and the constant
K

(mass growth rate coe$cient) of Eq. (1) can be

obtained from the relations
g"
2FC
"
3
"
A
''
#
C
"
C$
"
CQ `
"
"1.00
and
K

"!
CQ
"
A
''
C
"
"0.00056g (cm` min (C)).
The linear growth rate coe$cient k

can then be
calculated from K

with the following equation:

k

"K

F
3
"1.4E-07m(s (C)).
With supersaturation in dimensionless form,
k

"k

CH"3.79E-06 m/s.
5. Results and discussion
The results for several systems studied are
tabulated in Tables 2}6 in the order of potassium
alum, copper sulfate pentahydrate, adipic acid in
aqueous solution, adipic acid in ethanol and tere-
pthalic acid in 90% by weight acetic acid solution,
respectively. The growth orders g are calculated at
every isothermal temperature the experiments are
performed. The mass and linear growth rates coe$-
cients, K

and k

, respectively, are then calculated

with the g obtained. The linear growth rate
coe$cients are presented as k

with units of m/s

and supersaturation expressed in dimensionless
form. This ensures the consistency of the units
for the growth coe$cients obtained from various
sources.
The results from the present work for the systems
potassium aluminum sulfate dodecahydrate and
copper sulfate pentahydrate, obtained at 253C, are
compared to those from literature. A growth order
of 0.86 ($0.014) corresponding to a linear growth
rate coe$cient of 1.07E-05 ($7.62E-06) m/s was
obtained for potassium aluminum sulfate
dodecahydrate. The growth orders ranging from
0.9 to 1.61 were obtained from di!erent sources
[17}23] with corresponding growth rate coe$-
cients ranging from 8.60E-05 to 1.58E-08m/s for
temperatures ranging from 25 to 323C as sum-
marized in Table 2. A growth order of 1.06
($0.075) corresponding to a linear growth rate
coe$cient of 2.866E-05 ($7.11E-06) m/s was ob-
tained for copper sulfate pentahydrate. Growth or-
ders from literature ranged from 1.00 to 1.82
[24}29] with corresponding growth rate coe$-
cients ranging from 1.15E-08 to 7.64E-06m/s for
temperatures ranging from 25 to 303C as sum-
marized in Table 3.
The di!erence in growth orders has a direct e!ect
on the values of the growth rate coe$cients. Figs. 4
and 5 show an approximate comparison of growth
rates and supersaturation using the simple po-
wer-law equation R
'
"k

(), where "C/C*.

Though the values of the growth rates are not
absolutely accurate, they are nonetheless similar to
those obtained from literature. The following
points are to be kept in mind when comparing the
values from di!erent sources:
R. Mohan et al. / Journal of Crystal Growth 212 (2000) 489}499 495
Table 2
Comparison of growth order g and linear growth rate coe$cient k

of potassium aluminum sulfate dodecahydrate

S. no Temperature (3C) g k

(m/s) Source
1 25 0.86 ($0.014) 1.07E-05 ($7.62E-06) Present work
2 32 1.39 1.88E-06 Ref. [17]
3 32 1.50 8.36E-06 Ref. [18]
4 25 1.61 6.19E-06 Ref. [19]
5 30 0.90 1.58E-08 Ref. [20]
6 25 1.19 8.87E-07 Ref. [21]
7 25 1.48 3.66E-06 Ref. [22]
8 32 1.23 8.60E-05 Ref. [23]
Table 3
Comparison of growth order g and linear growth rate coe$cient k

of copper sulfate pentahydrate

S. no Temperature (3C) g k

(m/s) Source
1 25 1.06 ($0.075) 2.86E-05 ($7.11E-06) Present work
2 28 1.65 7.64E-06 Ref. [24]
3 30 1.00 8.12E-07 Ref. [25]
4 30 1.00 3.32E-06 Ref. [26]
5 27.8 1.26 1.77E-06 Ref. [27]
6 30 1.60 1.15E-08 Ref. [28]
7 25 1.82 1.30E-06 Ref. [29]
Fig. 4. Growth rates versus supersaturation of potassium alumi-
num sulfate dodecahydrate.
Fig. 5. Growth rates versus supersaturation of copper sulfate
pentahydrate.
E initial sizes of the crystals are di!erent;
E di!erent growth orders obtained;
E information on stirring speeds;
E di!erence in initial supersaturation;
E growth maybe overall or for a particular face;
E the growth orders and the growth rates corres-
pond to di!erent growth rate equations;
E di!erence in the process conditions.
496 R. Mohan et al. / Journal of Crystal Growth 212 (2000) 489}499
Table 4
Growth kinetic data for aqueous adipic acid
Temperature (3C) g k

(m/s)
20 0.82 ($0.06) 1.05E-06 ($2.68E-07)
30 0.87 ($0.09) 1.37E-06 ($5.33E-07)
40 0.85 ($0.07) 1.27E-06 ($8.14E-07)
50 0.92 ($0.012) 1.29E-06 ($1.43E-07)
60 0.96 ($0.16) 1.27E-06 ($3.84E-07)
70 1.04 ($0.00) 1.81E-06 ($3.65E-07)
80 0.89 ($0.21) 1.64E-06 ($9.36E-07)
100 0.92 ($0.05) 1.97E-06 ($6.73E-07)
Table 5
Growth kinetic data for adipic acid in ethanol
Temperature (3C) g k

(m/s)
0 0.89 ($0.10) 1.87E-06 ($2.71E-07)
10 0.81 ($0.004) 1.74E-06 ($2.75E-07)
20 0.86 ($0.06) 2.45E-06 ($1.01E-06)
30 0.88 ($0.06) 2.28E-06 ($5.16E-07)
40 0.92 ($0.14) 2.33E-06 ($1.25E-07)
50 0.94 ($0.09) 3.24E-06 ($7.82E-07)
Fig. 6. Arrhenius plot: adipic acid in water.
Fig. 7. Arrhenius plot: adipic acid in ethanol.
It is interesting to note that the values obtained
in this work are among the higher values reported
when compared with literature values in Figs. 4 and
5. This is surprising since there is no stirring in the
DSC pan and the possibility of mass transfer con-
trol.
David and Villermaux [30] studied the crystalli-
zation of aqueous adipic acid in a semi-batch cry-
stallizer and obtained a growth order of 2. The
growth orders obtained in the study of adipic acid
in water are 0.82 ($0.06), 0.87 ($0.09), 0.85
($0.07), 0.92 ($0.012), 0.96 ($0.16), 1.04
($0.00), 0.89 ($0.21) and 0.92 ($0.05) for the
temperatures of 20, 30, 40, 50, 60, 70, 80 and 1003C,
respectively. The corresponding values of growth
rate coe$cients are 1.05E-06 ($2.68E-07), 1.37E-
06 ($5.33E-07), 1.27E-06 ($8.14E-07), 1.29E-06
($1.43E-07), 1.27E-06 ($3.84E-07), 1.81E-06
($3.65E-07), 1.64E-06 ($9.36E-07) and 1.97E-06
($6.73E-07). The values of growth orders ob-
tained for the system adipic acid in ethanol are 0.89
($0.10), 0.81 ($0.004), 0.86 ($0.06), 0.88
($0.06), 0.92 ($0.14) and 0.94 ($0.09) for the
temperatures 0, 10, 20, 30, 40 and 503C, respective-
ly. The corresponding growth rate coe$cients are
1.87E-06 ($2.71E-07), 1.74E-06 ($2.75E-07),
2.45E-06 ($1.01E-06), 2.28E-06 ($5.16E-07),
2.33E-06 ($1.25E-07) and 3.24E-06 ($7.82E-07).
The results are summarized in Tables 4 and 5,
respectively.
The activation energies are calculated from the
Arrhenius plots of k

versus 1/ (Figs. 6 and 7) for

the systems: adipic acid in water and adipic acid in
ethanol. The activation energies obtained for the
systems are 6.31 and 7.39 kJ/mol, respectively.
In order to demonstrate the feasibility of this
experimental technique at very high temperatures
under pressure, the system terephthalic acid in
90% acetic acid and 10% water was studied at
R. Mohan et al. / Journal of Crystal Growth 212 (2000) 489}499 497
Table 6
Growth kinetic data for terepthalic acid in 90% by weight acetic
acid
Temperature (3C) g k

(m/s)
127 1 3.72E-07
162 1 9.24E-07
192 1 2.23E-06
Fig. 8. Arrhenius plot: terepthalic acid in 90% by weight acetic
acid.
temperatures reaching 1923C. High-temperature
solubility data for this system exist because of its
commercial importance and the fact that industrial
crystallization processes operate with terephthalic
acid at temperatures up to 3003C. The growth rates
obtained are 3.72E-07, 9.24E-07 and 2.23E-06 m/s
for temperatures of 127, 162 and 1923C, respective-
ly. A growth order of 1 was obtained at all temper-
atures. The results are summarized in Table 6. The
activation energy obtained from the Arrhenius plot
of k

versus 1/ from Fig. 8 was 42.27 kJ/mol.

An obvious weakness of this technique is the
curve "tting of the desupersaturation data to a sec-
ond-order polynomial introduces error in the "nal
results. Previous work has shown that the initial
part of the desupersaturation curve is a!ected by
mixing [7], reducing the accuracy of this method.
The lack of mixing in the DSC pans, while eliminat-
ing this reported e!ect introduces other errors due
to the lack of mixing and other possible mass trans-
fer control. The DSC technique, however, is a useful
tool for estimation of crystal growth kinetics when
very small amounts of sample are available and
or data are needed at high temperatures and
pressures.
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