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Kinetics of crystal growth of mirabilite in aqueous supersaturated solutions

Article in Journal of Crystal Growth · January 2012

DOI: 10.1016/j.jcrysgro.2011.11.007

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 Journal of Crystal Growth 338 (2012) 189–194

Contents lists available at SciVerse ScienceDirect

Journal of Crystal Growth

journal homepage: www.elsevier.com/locate/jcrysgro

Kinetics of crystal growth of mirabilite in aqueous supersaturated solutions

A.I. Vavouraki a,n, P.G. Koutsoukos b
a
Department of Chemical Engineering, University of Patras, University Campus, Karatheodori 1, GR 26500 Patras, Greece
b
Institute of Chemical Engineering and High Temperature Chemical Processes, Stadiou Str., Platani, P.O. Box 1414, GR-26504 Patras, Greece

a r t i c l e i n f o abstract

Article history: The crystallization of sodium sulfate decahydrate (Na2SO4  10H2O, mirabilite) from supersaturated
Received 23 February 2011 solutions was investigated using stable supersaturated solutions seeded with mirabilite seed crystals.
Received in revised form The experiments were done in batch, stirred reactors in which the supersaturated solutions were
7 September 2011
prepared either by dissolution of sodium sulfate anhydrous at 32 1C followed by cooling to 18 or 20 1C
Accepted 3 November 2011
or by mixing equal volumes of equimolar ammonium sulfate and sodium hydroxide solutions at 20 1C.
Communicated by B.A. Korgel
Available online 12 November 2011 Inoculation of the solutions supersaturated only with respect to mirabilite with seed crystals was
accompanied with temperature increase of the thermostated solution. Despite the fact that crystal growth
Keywords: was initiated with seed crystals, the process started past the lapse of induction times inversely proportional
A1. Supersaturated solutions
to the solution supersaturation. The rates of crystal growth were measured both from the temperature rise
A2. Crystal growth rates
and from the concentration–time profiles, which were linearly correlated. The measured crystal growth
A2. Growth from solutions
A3. Seed crystals rates showed a parabolic dependence on supersaturation at low supersaturations. For higher values
B1. Mirabilite this dependence changed to linear, a behavior consistent with the BCF spiral crystal growth model.
B1. Sodium sulfate decahydrate The morphology of the crystals growing at 20 1C showed typical prismatic habit, while at 18 1C when
crystallized from cooled sodium sulfate solutions changes in the crystal habit to a leaf like morphology
were observed.
& 2011 Elsevier B.V. All rights reserved.

1. Introduction (Na2SO4  10H2O, mirabilite) and the anhydrous (Na2SO4, thenardite)

The crystallization of sodium sulfate decahydrate (Na2SO4  10H2O,
mirabilite) in aqueous solutions is of concern mainly because of the
damaging effects on building materials and also because of its
significant industrial interest. The latter, stems from the fact that
sodium sulfate is used in home laundry detergents as a filler, in the
Kraft process of paper pulping, as a fining agent in glasses for bubble
removal in molten glass, in the manufacture of textiles where it
improves application of dyes because of charge reduction of the fabric
fibers, etc. [1,2]. Despite the extensive research done concerning the
crystallization conditions, understanding of the factors governing the
kinetics of formation of sodium sulfate hydrates and the underlying
mechanisms are still limited [3]. Considerable interest on the crystal-
lization of sodium sulfate hydrates has originated from the possibility
of use in energy storage applications [4]. Sodium sulfate is produced
globally either from mineral resources or to a large extent through
recovery from a number of processes where evaporative or cooling
crystallization is used [5–8]. Five forms of sodium sulfate have
been reported [9] but at ambient temperatures the decahydrate
n
Corresponding author. Tel.: þ30 2610997579.
E-mail addresses: kvavouraki@chemeng.upatras.gr,
katerina_vavouraki@lycos.com (A.I. Vavouraki).
salts are encountered, while the transient heptahydrate salt
(Na2SO4  7H2O) may be formed depending on the solution conditions
(temperature-supersaturation) [10,11].
During the crystallization of sodium sulfate from supersatu-
rated solutions a number of transient, metastable crystalline
phases differing in the extent of hydration have been recently
reported to form [10,12]. The crystallization of sodium sulfate has
been investigated in undercooled solutions [2], by salting out
processes in MSMPR crystallizers [13] by evaporation crystal-
lization through solution conductivity measurements [14], by
differential scanning calorimetry [15] and by growth in capillaries
[16]. A number of investigations have been concerned with the
crystallization of mirabilite in capillaries and/or pores in which
crystallization takes place due to local supersaturation develop-
ment [17–19]. The investigation of crystal growth kinetics of
mirabilite has been rather limited and mechanistic information is
based either on the measurement of the crystal growth of single
crystals in undercooled solutions by weight changes [2] or in
MSMPR by cooling crystallization using particle size distribution
measurements [20]. The limit for the labile region, where spon-
taneous precipitation of mirabilite takes place at 20 1C, has been
reported to be at concentrations of sodium sulfate equal to 3.7 m
[21]. The mechanism of crystal growth of mirabilite however in
supersaturated solutions, which are practically stable for very

0022-0248/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2011.11.007
190 A.I. Vavouraki, P.G. Koutsoukos / Journal of Crystal Growth 338 (2012) 189–194
long time periods (kinetic stabilization) has not yet clearly been
described. This supersaturation domain allows for the perfor-
mance of careful kinetics measurements and for the precise
determination of the effect that additives may have on the crystal
growth process. Clarification of the mechanism at specific opera-
tional conditions is of particular importance for the design of the
appropriate strategies to control the crystal growth of mirabilite
in aqueous media.
It is the aim of this study to obtain mechanistic information on
the crystal growth of mirabilite from supersaturated solutions
using the seeded growth technique as the most appropriate for
relatively low supersaturations. The results of measurements of
the crystallization kinetics of mirabilite in aqueous supersatu-
rated solutions, stable for very long time periods, were obtained
at temperatures of 18 and 20 1C. The two temperature values
selected were sufficient not only for the development of differ-
ences in the solution supersaturation but most important could
provide indications concerning changes in the morphology of the
mirabilite crystals, which grow out of the supersaturated solu-
tions. The investigation of the crystal growth kinetics at different
temperatures was limited to small differences due to the large
variation of mirabilite solubility with temperature [22]. Two
different methods of preparation of the supersaturated solutions
were tested: dissolution of sodium sulfate at higher temperature
and mixing ammonium sulfate and sodium hydroxide solutions.
The stability domain of the system was defined through a series of
preliminary experiments. Subsequent crystal growth experiments
were done in the stable domain of the supersaturated solutions
using mirabilite seed crystals.
2. Experimental
All experiments were done in a double walled jacketed reactor,
thermostated with circulating water from a programmable water-
bath (Cole-Parmer, Polyscience) equipped with heater and refrig-
erating unit ( 70.1 1C). The experimental setup is shown in Fig. 1.
The temperature of the water bath was initially set at 32 1C
and the reactor was thermostatted pumping the thermostatted
water through the walls of the glass jacket. The working solutions
were prepared in the reactor at this temperature (at which they
were undersaturated with respect to mirabilite) either by the
dissolution of anhydrous sodium sulfate (thenardite, Merck,
Puriss) in a carefully measured mass of water ( 70.01 g) or by
5
4 detected by our analytical methods could yield differences in the
6 supersaturation. The solubility of mirabilite crystals used to seed
1 the experimental temperatures 18 and 20 1C. The measurements
3
2 sodium sulfate were dissolved in 200 mL distilled water by
Fig. 1. Experimental set-up for the investigation of the crystallization of mirabilite
from aqueous supersaturated solutions. 1: heated–cooled circulating thermostat;
2: magnetic stirrer; 3: double walled water jacketed glass reactor; 4: thermo-
couple temperature sensor; 5: interface for data acquisition and transfer and
6: computer for data collection.
mixing equal volumes (100 mL each) of equimolar solutions
ammonium sulfate and sodium hydroxide, prepared from the
respective stock solutions. Solutions were stirred magnetically
throughout the crystal growth experiments. The stock solutions
were prepared from the respective crystalline solids (Merck, Pro
Analisi) using triply distilled water followed by filtration through
membrane filters (0.22 mm Millipore). The sodium hydroxide
solutions were standardized by titrations of potassium hydrogen
phthalate. The solutions were left in the reactor under magnetic
stirring (ca. 200 rpm) for 30 min at 32 1C. Next, the solution was
cooled at constant rate (0.5 1/min) to 18 and/or 20 1 depending on
the experimental conditions in each case. The temperature
reduction was sufficient for the development of supersaturation
with respect to mirabilite. The solutions were allowed to equili-
brate at the new temperature for at least 2 h under stirring. The
crystallization of mirabilite was initiated by inoculation of the
supersaturated solutions with mirabilite (ca. 250 mg, 71 mg)
seed crystals (mirabilite, 99þ %, Merck, A.C.S. reagent). The
stability of the seed crystals, kept at 4 1C at all times, was
regularly checked both with respect to water content and the
X-ray diffraction pattern to ensure that no dehydration took
place. Following the addition of the seed crystals, crystal growth
of mirabilite started past the lapse of very small yet reproducibly
(725 s) measured induction time. The crystal growth of mirabil-
ite, is exothermal at ambient pressure [23,24] and the process
was therefore followed through the temperature variation as a
function of time using a thermocouple connected to a computer
with the appropriate interface and recording software. In all
experiments of the present work, the crystal growth of mirabilite
on the seed crystals was rather fast (duration 2 min). During the
course of the crystallization, samples were withdrawn, filtered
through membranes filters (0.22 mm Millipore) in order to sepa-
rate the liquid from the solid. Solids on the filter were character-
ized and the filtrates were analyzed for sodium sulfate. Solids
were examined by scanning electron microscopy (SEM) and
characterized by powder X-ray diffraction (XRD, Philips 1830/40).
Both SEM and XRD analyses were done as fast as possible to avoid
dehydration of mirabilite. In SEM, due to the high vacuum, the
onset of dehydration could be clearly seen and at this point
morphology analysis was terminated. The sodium sulfate con-
centration analysis, during the course of crystal growth experi-
ments was done by evaporation of the liquid (water) in weighing
crystal vials at 80 1C. The respective mass was measured until
constant weight. Duplicate analyses were done by conductivity
titrations of the filtrates with standard barium nitrate solutions.
Since mirabilite crystals used to seed the solutions were
obtained commercially, their solubility was determined, since it
was possible that the presence of impurities, which could not be
solubility thus leading to erroneous calculations of the solution
the supersaturated solutions in the present work was measured at
were done approaching equilibrium from both under- and super-
saturated solutions. In the former case seed crystals were intro-
duced in undersaturated solutions and were allowed to reach
equilibrium, while in the latter mirabilite was allowed to reach
equilibrium from supersaturated solutions past seeded growth.
More specifically, accurately weighted amounts of anhydrous
successive solid additions, until no more salt could be dissolved.
In the case of supersaturated solutions mirabilite (250 mg) was
introduced in stable supersaturated solutions close to the esti-
mated (literature values) equilibrium. The mirabilite crystals,
with a high surface to volume ratio, required only a short time
to reach equilibrium. Samples were withdrawn over a time period
 A.I. Vavouraki, P.G. Koutsoukos / Journal of Crystal Growth 338 (2012) 189–194 191

of 24 h in order to confirm the constancy of the solute concentra-
tion. In both cases, the precise concentration of sodium sulfate in
the bulk solutions was measured by gravimetric analysis and the
solubility of sodium sulfate was found to be equal to 1.03 at 18 1C
( 70.03) and 1.23 ( 70.05) mol kg  1 H2O at 20 1C. Solubility
values were in good agreement with solubility values reported
earlier [22,25].
The temperature– time and concentration–time profiles were
used for the calculation of the crystal growth rates of mirabilite at
different supersaturations (RT and RC, respectively). The reported
values are the average of experiments done in triplicate. The
supersaturations investigated in the experiments of the present
work with respect to mirabilite ranged between 0.24–0.66 at
18 1C and 0.18–0.54 at 20 1C.
3. Results and discussion
The thermodynamic driving force for the crystallization of
mirabilite is the solution supersaturation, S. Assuming that at
relatively small deviations from equilibrium (as in the present
work) activity coefficients in the supersaturated solutions and at
equilibrium are the same, S may be defined as
ms
S¼
m1
where ms and mN are the solute molal concentrations in the
supersaturated solution and at equilibrium, respectively. The
relative supersaturation, s, is
cs c1
s¼ ¼ S1
c1
prepared mixing equimolar solutions of ammonium sulfate and
sodium hydroxide as described in the experimental section.
Following the introduction of seed crystals in the supersaturated
solutions and past a short induction time the solution tempera-
ture increased and after reaching a maximum decreased to return
to the initial temperature of the thermostated reactor. Sampling
and analysis for the concentration of the remaining in solution
sodium sulfate during the time corresponding to the temperature
changes, showed that this time period corresponded to the de-
supersaturation of the solution, which returned to a point close
but not exactly to equilibrium. The temperature and concentra-
tion changes of the sodium sulfate concentration in solution for a
typical experiment are shown in Fig. 3.
The temperature increase, Dy, in the solution following the
addition of seed crystals in the supersaturated solutions was
attributed to the heat of crystallization. In all cases the tempera-
ture rise was proportional to the solution supersaturation, as may
be seen in Fig. 4.
The experimental conditions (i.e. temperature and concentra-
tions) were such that heat transfer effects in the process of crystal
growth may be neglected [26]. The induction times preceding the
ð1Þ 3.0
2.5
2.0
ð2Þ
Δθ/°C

The supersaturated solutions were prepared using the infor- 1.5

mation of the solubility of the various hydrate salts, so that the
working solutions were supersaturated exclusively with respect 1.0
to mirabilite to avoid the potential formation of transient phases.
The domain of the supersaturation range of the experiments done
0.5
in the present work is shown in Fig. 2.
As may be seen, the only sodium sulfate possible thermo-
dynamically to form in our experimental conditions was the 0.0
decahydrate. The relative supersaturation range for this salt was 0 5 10 15 20 25 30
between s ¼0.24–0.66 for 18 1C and 0.18–0.54 at 20 1C for t / min
solutions prepared by dissolution of anhydrous sodium sulfate
at 32 1C, and between 0.12 and 0.46 for supersaturated solutions 2.0

4.0
1.8
Thenardite
m Na2SO4/mol Kg-1

1.6
3.0
Solubility / mol Kg-1

Heptahydrate

1.4

2.0 Mirabilite
1.2

1.0 1.0
0.0 0.5 1.0 1.5 2.0
t / min
10 15 20 25 30 35 Fig. 3. Temperature– and concentration–time profiles for the seeded growth of
Temperature /°C sodium sulfate decahydrate from supersaturated solutions; 20 1C, s ¼ 0.38.
(a) Temperature–time profile following the introduction of mirabilite seed
Fig. 2. Solubility isotherms for sodium sulfate. Solubility data for mirabilite and crystals. Dashed line indicates the slope of the rising part, which was used for
thenardite from Ref. [23] and for heptahydrate from Ref. [13]; (J) solubility the calculation of the rates of crystal growth; (b) concentration–time profile of the
measurements of the present work; (): crystal growth experiments of mirabilite sodium sulfate decahydrate concentration remaining in the solution for the
at 18 1C (Table 1); () crystal growth experiments of mirabilite at 20 1C (Table 1). experiment corresponding to (a).
192 A.I. Vavouraki, P.G. Koutsoukos / Journal of Crystal Growth 338 (2012) 189–194

4.0 15

3.5
1
3.0 2

3 10
2.5

RT / °C min-1
4
Δθ/°C

2.0 5

6
1.5 7
8 5
1.0
9
10
0.5

0.0
0
0 5 10 15 20 25 30 0 30 60 90
t / min G / ms-1
Fig. 4. Crystal growth of sodium sulfate decahydrate following seeding in super- Fig. 6. Seeded growth of sodium sulfate decahydrate from supersaturated solu-
saturated solutions with mirabilite seed crystals at 20 1C, at different values of tions: correlation between the rate measured from the respective rate of the
relative supersaturation, s; 1:0.54; 2:0.50; 3:0.46; 4:0.42; 5:0.38; 6:0.34; 7:0.30; temperature rise, following the addition of mirabilite crystals, RT, and the linear
8:0.26; 9:0.22 and 10:0.18. growth rate, G, calculated from the decrease of the solute concentration as a
function of time; supersaturated solutions prepared by the dissolution of sodium
sulfate at 32 1C: () 18 1C; (~) 20 1C and (J) 20 1C, solutions prepared mixing
3.0
ammonium sulfate and sodium hydroxide.

2.5
of sodium sulfate decahydrate. For the same temperature, the
linear relationship is valid regardless of the method of prepara-
2.0
tion of the supersaturated solutions.
The initial experimental conditions and the crystal growth
1.5
Δθ/°C

rates measured from the concentration–time profiles are sum-

marized in Tables 1 and 2. The linear growth rates, G, were
1.0 calculated from the respective mass rates, RC, using Eq. (3) [28]
τ 3a
0.5 RC ¼ rmirabilite G ð3Þ
S b

0.0
0.0 0.5 1.0 1.5 2.0
t / min
Fig. 5. Crystal growth of mirabilite from supersaturated solutions prepared from
sodium sulfate solutions, on mirabilite seed crystals at 20 1C, s ¼ 0.38. Plot of the
change of solution temperature as a function of time; S: addition of seed crystals
and t: induction time preceding crystallization.
onset of crystal growth and the rates of crystal growth were
measured from the temperature–time profile variation for each
experiment as shown in Fig. 5.
Induction times preceding crystal growth in seeded growth of
sparingly soluble salts has been reported in the literature and has
been used as a tool for the investigation of the mechanism of
crystal growth, in combination with results from experiments in
which the precipitation was spontaneous [27]. The crystal growth
rates were doubled upon doubling the amount of the inoculating
seed crystals, suggesting that it was the seed crystals, which grew
and that secondary nucleation was absent.
Measurements of the rates of crystal growth done measuring
both the rate of temperature rise, RT, and the rate of concentration
decrease of sodium sulfate in the supersaturated solutions, RC (or
the corresponding linear growth rate defined in Eq. (3)) showed a
linear relationship, as may be seen in Fig. 6. This linear relation-
ship, entirely empirical, suggested that it is possible, at least for
the experimental conditions of the present work (temperature
and supersaturation range) to calculate mass crystal growth rates
from the rate of temperature rise as a result of the crystallization
where 3a/b is a shape factor equal to 1 (cubes and spheres) and
rmirabilite is the density of the mirabilite crystals.
The plots of the linear growth rates as a function of the relative
supersaturation, shown in Fig. 7, suggested that there is a
parabolic dependence at the low supersaturation range followed
by linear at higher supersaturations in agreement with the
prediction of the Burton–Cabrera–Frank model of spiral growth
[29]. This complex dependence of the growth rates on the relative
supersaturation for both systems investigated, suggested that the
mechanism is surface diffusion controlled.
It is interesting to note that large differences in the measured
rates were observed at the different temperatures measured,
apart only by 2 1C. These differences implied large values of the
corresponding apparent activation energy. The small temperature
difference investigated was justified by the fact that the solubility
of mirabilite is strongly affected by temperature. The rate deter-
mining step in the crystal growth of mirabilite from supersatu-
rated solutions is surface diffusion, suggesting the possibility to
control kinetics by changes of the surface of mirabilite, which
may be done e.g. by the adsorption of compounds capable of
electrostatic or other type of interactions at the solid/water
interface [30]. The strong temperature dependence (high appar-
ent activation energy) corroborated further the mechanistic con-
clusions drawn from the kinetics measurements. Finally, it is also
interesting to note that the source of the crystallizing mirabilite
lattice ions did not seem to play an important role at low
supersaturations, while at higher values the rates measured were
lower exceeding the experimental error710%.
The magnitude of the crystal growth rates of mirabilite
measured in our experiments were comparable with the rates
 A.I. Vavouraki, P.G. Koutsoukos / Journal of Crystal Growth 338 (2012) 189–194 193

Table 1
Seeded crystal growth experiments of mirabilite (250 mg mirabilite seed crystals),
8.0x10-5
from supersaturated solutions prepared by dissolution of thenardite at 32 1C at
different relative supersaturation values, s, induction times, t, maximum change
in temperature due to crystallization, Dy, rate of crystal growth measured from

Growth Rate / m s-1

temperature–time profiles, RT and rate of crystal growth measured from the 6.0x10-5
concentration–time profiles, RC.

r s (s) Dh (1C) RT (1C min  1) RC (mol g  1 min  1) G (  10  6 m s  1)

4.0x10-5
18 1C
0.24 90 0.28 0.11 0.038 1.2
0.30 30 0.64 0.39 0.042 1.3
0.36 24 1.02 0.85 0.050 1.6
2.0x10-5
0.42 12 1.35 1.13 0.062 2.0
0.48 7 1.92 2.00 0.080 2.6
0.54 6 2.32 3.88 0.100 3.2
0.60 o6 2.68 5.59 0.114 3.6 0.0 0.1 0.2 0.3 0.4
0.66 o6 2.95 8.21 0.140 4.5
Relative supersaturation / σmirabilite
20 1C
0.18 70 0.48 0.19 0.110 3.5 Fig. 7. Plots of the rate of crystal growth of sodium sulfate decahydrate as a
0.22 42 0.76 0.97 0.300 9.6 function of the relative solution supersaturation. Seeded crystal growth from: ()
0.26 36 1.10 1.60 0.400 12.8 supersaturated solutions prepared from the dissolution of sodium sulfate at 20 1C;
0.30 36 1.34 1.75 0.550 17.6 (m) supersaturated solutions made mixing equimolar quantities of (NH4)2SO4 and
0.34 30 1.70 2.65 0.750 23.9 NaOH at 20 1C and (~) supersaturated solutions prepared from the dissolution of
0.38 28 1.98 3.80 1.200 38.4 sodium sulfate at 18 1C.
0.42 24 2.36 7.50 1.500 48.0
0.46 22 2.63 9.00 1.800 57.5
0.50 12 3.00 12.00 2.300 73.5
2000
0.54 10 3.29 13.00 2.600 83.1 3,83

1600
Table 2
Seeded crystal growth experiments of mirabilite (250 mg mirabilite seed crystals),
Intensity / a.u.

from supersaturated solutions prepared by mixing equimolar (NH4)2SO4 and 1200

NaOH solutions at various relative supersaturation values, s with respect to 5.49
sodium sulfate salt at 20 1C, induction times, t, maximum change in temperature
due to crystallization, Dy, rate of crystal growth measured from temperature–time 2,52
profiles, RT and rate of crystal growth measured from the concentration–time 800
profiles, RC.
3.11
r s (s) Dh(1C) RT (1C min  1) RC (mol g  1 min  1) G (  10  6m s  1)
400
20 1C
0.12 192 0.08 0.01 0.01 0.2
0.15 114 0.17 0.04 0.03 1.1 0
0.18 48 0.33 0.18 0.09 2.9
0.20 48 0.39 0.21 0.15 4.7
10 20 30 40 50 60 70 80
0.22 18 0.72 0.43 0.23 7.5
0.24 18 0.87 1.07 0.29 9.4
2θ/°
0.26 12 1.04 1.50 0.40 12.8
Fig. 8. Powder X-Ray Diffraction pattern for mirabilite collected following seeded
0.28 o 12 1.20 1.76 0.50 16.0
crystal growth in supersaturated solutions at 20 1C. d spacing values in Å.
0.32 o 12 1.34 2.20 0.70 22.4
0.34 o 12 1.60 2.69 0.74 23.7
0.41 o 12 2.26 6.37 1.40 44.7
0.46 o 12 2.60 7.97 1.70 54.3 temperature. The molecular volume was calculated from Eq. (5):
FW Mirabilite
um ¼ ð5Þ
NA rmirabilite n

of crystal growth of sodium sulfate decahydrate measured in
cooling crystallization from supersaturated solutions [2,31] and in
MSMPR crystallizer [1]. The dependence of the induction time on
the solution supersaturation showed a typical profile as expected
from the classical nucleation theory [28,32] according to which
the relationship between the logarithm of the induction time and
the inverse of the square of the logarithm of the relative super-
saturation is linear:
16pu2m g3s 1 ture is both expected and rather large for a temperature variation
log t ¼ A þ
3ðkTÞ3 ðlog SÞ2
In Eq. (4), A is a constant, 16p/3 is a shape factor corresponding
to spherical shape of the new nuclei, um the molecular volume of
mirabilite, gs is the surface tension of the new nuclei developing
on the surface, k Boltzmann’s constant and T the absolute
where FWMirabilite and rMirabilite are the formula weight and the
density of the solid (322.20 and 1.49 g cm  3, respectively), NA
Avogadro’s number and n the number of ions in the formula of
mirabilite [33]. The values calculated from the linear fit of the
experimental data according to Eq. (4) yielded values for the
surface energy of 3.9 and 2.1 mJ m  2 for 18 and 20 1C, respec-
tively. The low values were anticipated since the nucleation is
mainly heterogeneous on the inoculating seed crystals. The trend
however of decreasing surface energy with increasing tempera-
ð4Þ
of only 2 1C.
The crystalline solid was identified as mirabilite by powder X
ray diffraction (XRD) as may be seen in the spectrum shown in
Fig. 8, where the reflections corresponding to d ¼5.49, 3.83, 3.48
and 3.11 Å typical of synthetic mirabilite (ICDD 11-647). The XRD
patterns obtained were in agreement with the results of the
194 A.I. Vavouraki, P.G. Koutsoukos / Journal of Crystal Growth 338 (2012) 189–194
Fig. 9. Scanning electron micrographs of mirabilite crystallized on mirabilite seed
crystals grown at (a) 20 1C and (b) 18 1C.
analysis of the crystalline solids by Correcher et al. [34] during the
thermal transformation of mirabilite to thenardite.
The inconsistency of the relative intensities observed and the
extra reflections may be attributed to phase changes in the
specimen holder during the recording of the XRD patterns. The
morphology of the crystallized mirabilite showed the typical
prismatic habit [9] at 20 1C as may be seen in Fig. 9a, while at
18 1C a different rose-like crystal habit was seen (Fig. 9b).
4. Conclusions
The kinetics of crystal growth of sodium sulfate decahydrate at
18 and 20 1C from stable supersaturated solutions were investigated
with the highly reproducible, seeded crystal growth methodology.
The kinetics of crystal growth were estimated by the temperature
rise in an isothermal reactor monitoring carefully the temperature
variation with time. The dependence of the crystal growth kinetics
measured on the respective solutions supersaturation, suggested a
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surface diffusion controlled mechanism, consistent with the spiral
growth model. The method of preparation of the supersaturated
solutions did not affect the kinetics at low supersaturations. The
effect of temperature on the rate constants was significant.
Acknowledgments
Financial support from the EC, FP6 Programme Contract no.
SSP1-CT-2003-501571-SALT CONTROL is acknowledged.
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