See

discussions, stats, and author profiles for this publication at: http://www.researchgate.net/publication/222149607

Kinetics of gypsum formation and growth during

the dissolution of colemanite in sulfuric acid

ARTICLE in JOURNAL OF CRYSTAL GROWTH · OCTOBER 2001

Impact Factor: 1.69 · DOI: 10.1016/S0022-0248(01)01525-1

CITATIONS DOWNLOADS VIEWS

29 335 433

3 AUTHORS, INCLUDING:

Inci Eroglu Saim Özkar

Middle East Technical University Middle East Technical University
112 PUBLICATIONS 1,950 CITATIONS 279 PUBLICATIONS 3,322 CITATIONS

SEE PROFILE SEE PROFILE

Available from: Saim Özkar

Retrieved on: 22 June 2015
 Journal of Crystal Growth 231 (2001) 559–567

Kinetics of gypsum formation and growth during the

dissolution of colemanite in sulfuric acid
E. Çetina, I. .
’ Erog& lua, S. Ozkarb,
*
a
Department of Chemical Engineering, Middle East Technical University, 06531 Ankara, Turkey
b
Department of Chemistry, Middle East Technical University, 06531 Ankara, Turkey

Received 18 May 2001; accepted 24 May 2001

Communicated by M. Schieber

Abstract

One of the most important boron minerals, colemanite, is dissolved in aqueous sulfuric acid to produce boric acid
whereby gypsum is formed as byproduct. Filtration of gypsum has an important role in boric acid production because
gypsum affects the efficiency, purity and crystallization of boric acid. The formation and growth kinetics of gypsum
during the dissolution of colemanite in aqueous sulfuric acid were studied in a batch reactor by varying the temperature
(60–901C), stirring rate (150–400 rpm), and initial concentrations of the reactants. The initial CaO/H2SO4 molar ratio
was varied between 0.21–0.85 by keeping the initial concentration of sulfate ion at [SO2
4 ]o=0.623 mol/l, and 0.85–3.41
by keeping the initial concentration of colemanite at [B2O3]o=0.777 mol/l. The crystallization of gypsum from the
solution was followed by monitoring the calcium ion concentration in the solution as it is decreased by the formation of
calcium sulfate precipitate. The calcium ion concentration in the liquid phase first undergoes a rapid exponential decay
and then slowly approaches an asymptotic value of the saturation concentration at the respective temperature.
The saturation concentration decreases with the increasing temperature from 5.2 mmol/l at 601C to 3.1 mmol/l
at 801C, however, further increase in the temperature up to 901C causes an increase in the saturation concentration to
5.1 mmol/l. The stirring rate was found to have no significant effect on dissolution in the range of 150–400 rpm. The
minimum saturation concentration of the calcium ion was obtained at 801C when the initial CaO/H2SO4 molar ratio is
0.85. The boric acid concentration in the solution decreases with the decreasing initial concentration of sulfuric acid.
After the fast dissolution reaction of colemanite in aqueous sulfuric acid, the nucleation of the gypsum crystals first
occurs from the supersaturated solution and then the crystals grow on these nuclei. The needle like crystals become
wider and taller on prolong crystallization. The rate of gypsum crystallization reaction was second order with respect to
saturation level. The evaluation of the kinetic data in an Arhenius plot gives an activation energy of 3472 kJ/mol for
the crystal growth of gypsum from the supersaturated solution obtained by dissolution of colemanite in aqueous
sulfuric acid. r 2001 Elsevier Science B.V. All rights reserved.

Keywords: A1. Optical microscopy; A1. Solubility; A1. Supersaturated solutions; A2. Growth from solutions; B1. Calcium
compounds; B1. Inorganic compounds

*Corresponding author. Tel.: +90-312-210-3212; fax: +90-312-210-1280.

.
E-mail address: sozkar@metu.edu.tr (S. Ozkar).

0022-0248/01/$ - see front matter r 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 1 ) 0 1 5 2 5 - 1
560 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567
1. Introduction
Boron is the most important element in the
world from both strategic and industrial point of
view. Although the element is not used directly, its
compounds have a wide range of applications
almost in all the manufacturing areas, except food.
More than one half of the boron compounds is
consumed in the production of glass and fibers of
various kinds, e.g. in borosilicate glasses. Boron
compounds are also widely used in detergents, fire
retardants, nuclear reactors, agriculture, and
material processing [1]. Boric acid is the most
commonly used boron compound which has a
surprising variety of applications in both industrial
and consumer products [2] and serves as a source
of B2O3 in many fused products including textile
fiber glass, optical and sealing glasses, heat-
resistant borosilicate glass, ceramic glazes, and
porcelain enamels [3]. Boric acid is also used as
starting material in the preparation of many boron
chemicals including synthetic organic borate salts,
boron phosphate, fluoroborates, boron trihalides,
borate esters, boron carbide, and metal alloys such
as ferroboron.
Boron is oxophilic and, therefore, occurs
primarily as oxide (borates) in nature. Boron
minerals occur in a few locations in the world.
The largest reserves of boron minerals in the world
are in the western part of Turkey [4]. Colemanite
(2CaO  3B2O3  5H2O), which is a kind of hydrated
calcium borate, is one of the most important
boron minerals. Boric acid is produced in Turkey
and Europe mainly from the reaction of colema-
nite with sulfuric acid [5]. The overall reaction is as
follows:
2CaO  3B2 O3  5H2 O þ 2H2 SO4 þ6H2 O
-2CaSO4  2H2 O þ 6H3 BO3
Calcium sulfate dihydrate (Gypsum, Ca-
SO4  2H2O) crystallizes in the reactor. Filtration
of gypsum crystals after the reaction is a crucial
process in the production of boric acid in high
purity and with high efficiency, as the subsequent
crystallization of boric acid from the supernatant
solution is affected by contaminations.
Although six different calcium sulfate crystal
phases have been claimed to exist [6], the forma-
tion of calcium sulfate in aqueous solutions,
depending on the conditions of temperature and
the concentration of the dissolved ions, may yield
only three forms: Calcium sulfate dihydrate
(Gypsum, CaSO4  2H2O), calcium sulfate hemi-
hydrate (CaSO4  1/2H2O), and calcium sulfate
anhydrite (CaSO4) [7]. Calcium sulfate dihydrate
is either found in nature as a mineral [8] or
precipitated from aqueous solutions [9], as well as
from the hydration of calcium sulfate hemihydrate
[10,11]. Calcium sulfate dihydrate forms small
needle-like crystals having a monoclinic, prismatic
structure with water molecules between the cal-
cium and sulfate ions in the unit cell. The crystal
structures of calcium sulfate dihydrate and calcium
sulfate hemihydrate differ from each other because
of the amount of lattice water [12]. The formation
of calcium sulfate dihydrate from aqueous solu-
tion has been investigated by using different
structural techniques such as microscopy, IR
spectroscopy, differential scanning calorimetry,
and X-ray diffraction [13–16]. The solubility of
calcium sulfate forms including gypsum decreases
with increasing temperature [17–19], a fact that is
responsible for the formation of calcium sulfate
scale on heat exchanger surfaces [20]. Thus the
temperature is an important parameter affecting
the precipitation of calcium sulfate in the super-
saturated solutions [21]. The solubility of calcium
sulfate also depends on the concentration of the
ions present in the solution as expected. However,
a study on the solubility of calcium sulfate
dihydrate in a temperature range of 52–901C in
solutions containing 0–21% boric acid (H3BO3) has
shown that the solubility of gypsum is independent
of H3BO3 concentration, but is strongly affected by
the H2SO4 concentration in H3BO3 solutions [22].
The crystal growth kinetics of calcium sulfate
ð1Þ
dihydrate in aqueous solutions has been studied
under various conditions; in supersaturated solu-
tions over the temperature range of 25–801C [21], at
heated metal surfaces [23], on the added seed
crystals [24], in the presence of polyelectrolytes [25],
phosphates [26], organophosphorus compounds
[12], polymers [27,28], sodium chloride [29], and
in low supersaturation [30].
Dissolution of the colemanite mineral in sulfuric
acid solutions, yielding a slurry of gypsum crystals
 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567
and boric acid, has been investigated in the
temperature range of 20–901C [31]. Although the
filtration of gypsum slurry has been carried out in
the production of boric acid on large scale, there
exist no study on the crystal growth kinetics of
calcium sulfate dihydrate in the dissolution of
colemanite with sulfuric acid in the literature. The
lack of kinetic data in this industrially important
field prompted us to start a study dealing with the
formation and growth of gypsum crystals in
dissolution of colemanite with the ultimate goal
of obtaining kinetic parameters which will be used
in designing the filtration of gypsum slurry leaving
the pure boric acid in the solution from which it
can be crystallized. Here we report the first results
of the investigation on the formation and growth
kinetics of gypsum during the dissolution of
colemanite with sulfuric acid in a batch reactor
by varying the temperature, stirring rate, and
initial concentrations of the reactants.
2. Experimental procedure
Materials Colemanite mineral (an average par-
.
ticle size of 2.5 cm, Hisarcık-Kutahya, Turkey) and
sulfuric acid (93% b.w.) were supplied by Eti
Holding A.S. , (Ankara, Turkey). The colemanite
was crushed in a jaw crusher, grinded in a hammer
mill, and then sieved. The particles smaller than
250 mm were used in the experiments. The chemical
composition of the colemanite mineral used is
Table 1
Composition of the colemanite used in the experiments,
determined by chemical analysis of the dried sample
Component (wt %)
B2O3 37.71
CaO 20.79
Na2O 0.65
MgO 2.16
Al2O3 1.79
SiO2 4.08
Fe2O3 0.82
SrO 0.69
TiO2 0.17
K2O 1.59
561
given in Table 1. All the other chemicals used in
the analysis were purchased in reagent grade from
Merck (Darmstadt, Germany).
Experimental setup and procedures The experi-
mental setup consists of a reactor, a mechanical
stirrer, a heating jacket, a thermocouple and a
temperature control unit. The reactor having an
inside diameter of 12 cm and a height of 30 cm (the
bottom section) is made up of borosilicate glass
’
(Ildam Kimya, Ankara, Turkey). The top section
of the reactor has three entrances; the one at the
center is for mixing by using a glass propeller.
Thermocouple is placed inside the reactor through
one of the other entrances. The last entrance is
used for taking samples out of the reactor by
means of a syringe.
A given amount of sulfuric acid was added into
one liter of distilled water in the reactor, yielding a
solution with the initial concentration of SO2
4 ion
in the range of 0.156–0.623 M. The reactor was
heated to the reaction temperature. Certain
amount of colemanite was fed into the reactor at
one lot, providing an initial concentration of B2O3
in the range of 0.194–0.777 M. This time was
considered as the starting point of the reaction.
The samples were taken in time intervals and
filtered through a blue band filter paper. The
percentage of solid phase in the solution was
determined as follows: The samples taken during
the experiment were first weighed and then filtered
immediately. The filtrates were first dried and then
weighed. The boric acid concentration of the liquid
phase was determined as follows: 2 ml sample
solution was transferred into a test tube by using a
2 ml glass-pipette. Two or three drops of concen-
trated hydrochloric acid and then 10 ml concen-
trated sulfuric acid were added into the solution.
After having mixed the solution for 30 min, 10 ml
of carmine solution was added into the solution
which was stirred for 1 h. The absorbance of the
solution was measured at 650 nm on a UV-vis
spectrophotometer (Jenway 6105). The absor-
bance values were converted to the concentrations
of boric acid by using the calibration curve
prepared by using standard solutions containing
known amount of H3BO3. The calcium ion
concentration was determined by Atomic Absorp-
tion Spectrophotometer (Philips PU 9200X).
562 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567

Micrographs of gypsum crystals were obtained

by a light microscope (Prior Laboratory Micro-
scope Model B 3000) that was connected online to
a computer by a Pro Series, high performance
CCD Camera. Images were analyzed by using the
analytical imaging software called Image Pro Plus
3.0 for Windows.
Experiments were performed at different tem-
peratures (60–901C), stirring rates (150–400 rpm),
and B2O3 to SO2
4 molar ratios (0.3–5).
Fig. 1. Variations in the calcium ion concentration during the
dissolution process of colemanite in aqueous sulfuric acid at
3. Results and discussion different temperatures (stirring rate 200 rpm; initial concentra-
tions are [B2O3]o=0.777 and [SO2
4 ]o=0.623 mol/l).

3.1. Dissolution of colemanite in aqueous sulfuric

acid

The colemanite mineral with a particle size

smaller than 250 mm were dissolved in sulfuric acid
at different temperatures 601C, 701C, 801C, and
901C under vigorous stirring. In course of each
dissolution process, concentrations of the boric
acid and the calcium ion as well as the amount of
the solid material in the reactor were determined at
certain time interval to follow the reaction between
the colemanite and the sulfuric acid. It was found
that the formation of boric acid is almost
completed within the first minute and then the
concentration of boric acid in the liquid phase
remains practically unaltered throughout the
experiment. As a result, the dissolution process
of colemanite in aqueous sulfuric acid is a very fast
reaction. However, it does not mean that the
formation and precipitation of calcium sulfate
crystals is as fast as the boric acid formation. The
latter reaction involves the nucleation and growth
of calcium sulfate, which might require longer time
than that needed for the formation of boric acid.
The crystallization of gypsum from the solution
can be followed by monitoring the calcium ion
concentration in the solution as it is decreased by
the formation of calcium sulfate precipitate. Fig. 1
illustrates the changes in calcium ion concentra-
tion during the dissolution process of colemanite
in aqueous sulfuric acid at different temperatures
(stirring rate 200 rpm; initial concentrations are
[B2O3]o=0.777 and [SO2
4 ]o=0.623 mol/l). The
calcium ion concentration in the liquid phase first
Fig. 2. Variations in the solid content of the reactor during the
dissolution process of colemanite in aqueous sulfuric acid at
different temperatures (stirring rate 200 rpm; initial concentra-
tions are [B2O3]o=0.777 and [SO2
4 ]o=0.623 mol/l).
undergoes a rapid exponential decay and then
slowly approaches an asymptotic value, which is
the saturation concentration at the respective
temperature. In agreement with the previous data,
the saturation concentration decreases with the
increasing temperature from 5.2 mmol/l at 601C to
3.1 mmol/l at 801C, however, further increase in
the temperature up to 901C causes an increase in
the saturation concentration to 5.1 mmol/l.
Fig. 2 illustrates the changes in the solid content
of the reactor during the dissolution process of
colemanite in aqueous sulfuric acid at different
temperatures (stirring rate 200 rpm; initial con-
centrations are [B2O3]o=0.777 and [SO2
4 ] o=
0.623 mol/l). In all of the experiments, the initial
amount of solid in the reactor is 12%. One
observes a fluctuation in the experimental results
due to the large uncertainty in the determination
 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567
of solid content especially at high temperature.
However, a general trend is recognizable; a rapid
increase in the solid content of the reactor to 14%
is observed within the first minute and then it
remains between 14–16% for all the experiments
except the one carried out at 801C in which the
solid content of the solution increases up to 18%.
This is in accordance with the fact that the
maximum amount of gypsum precipitate is ob-
tained at 801C. The small decrease in the solid
content with time may be attributed to the
precipitation of larger particles because of insuffi-
cient stirring.
In order to investigate the effect of stirring rate
on the dissolution of colemanite in aqueous
sulfuric acid, the experiments were performed
at 150, 200 and 400 rpm at 801C starting with
the initial concentrations of [B2O3]o=0.777 and
[SO2
4 ]o=0.623 mol/l). The results obtained shows
that the stirring rate does not have any significant
effect on dissolution in the range of 150–400 rpm.
Indeed, the calcium ion concentration shows
similar variations at all stirring rates and one
obtains the same solid content of the reactor at the
stirring rates of 200 and 400 rpm while the non-
uniform mixing at 150 rpm does not allow to take
a representative sample for the determination of
the solid content of the reactor. From the
observation that the dissolution of colemanite in
aqueous sulfuric acid is fast and independent of
the stirring rate in the range of 150–400 rpm, one
can conclude that the reaction is mass transfer
limited [32]. This is not unlikely for such a
heterogeneous reaction between a solid and a
liquid. The rate of the fast dissolution reaction is
limited by the rate of diffusion of the sulfuric acid
through the surface of the solid colemanite
particles, which is continuously refreshed as the
fast reaction proceeds.
Fig. 3 shows the variations in the concentration
of calcium ion depending on the initial CaO/
H2SO4 molar ratio during the dissolution of
colemanite in the sulfuric acid at 801C. The initial
CaO/H2SO4 molar ratio is varied between 0.21–
0.85 by keeping the initial concentration of sulfate
ion at [SO2
4 ]o=0.623 mol/l, and 0.85–3.41 by
keeping the initial concentration of colemanite at
[B2O3]o=0.777 mol/l. It is meaningful to consider
563
Fig. 3. Variations in the calcium ion concentration depending
on the initial CaO/H2SO4 molar ratio during the dissolution of
colemanite in aqueous sulfuric acid at 801C and a stirring rate
of 200 rpm. The initial CaO/H2SO4 molar ratio is varied
between 0.21–0.85 by keeping the initial concentration of
sulfate ion at [SO2

4 ]o=0.623 mol/l, and 0.85–3.41 by keeping
the initial concentration of colemanite at [B2O3]o=0.777 mol/l.
the saturation concentrations of the calcium ion.
The minimum saturation concentration of the
calcium ion is obtained when the initial CaO/
H2SO4 molar ratio is 0.85. Deviation from this
ratio causes a rapid increase in the saturation
concentration of calcium ion. These results in-
dicate the significance of the initial CaO/H2SO4
molar ratio for obtaining the maximum amount of
gypsum precipitate after the dissolution of cole-
manite in aqueous sulfuric acid.
The calcium ion concentrations obtained at the
beginning of reaction are much higher than the
saturation values and, therefore, can be considered
as the supersaturation concentration. Depending
on the initial CaO/H2SO4 molar ratio, the super-
saturation concentration of calcium ion varies
between 0.020–0.065 M. These values are in
accordance with the supersaturation concentration
of Ca2+ reported previously for the dissolution of
colemanite in aqueous sulfuric acid [31]. The
supersaturation concentration is between 0.02–
0.035 M, if the initial CaO/H2SO4 molar ratio is
0.85, for the dissolution of colemanite in aqueous
sulfuric acid at different temperature as shown in
Fig. 1. It is interesting to note that the saturation
concentration decreases to 0.0031–0.0052 M at the
end of these experiments.
Another key observation is that the boric acid
concentration in the solution decreases with the
564 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567

decreasing initial concentration of sulfuric acid.

This indicates that some colemanite remains
unreacted if the amount of sulfuric acid used is
less than that required to dissolve all the colema-
nite added (if the initial CaO/H2SO4 molar ratio is
greater than 0.85).

3.2. Crystal growth of calcium sulfate dihydrate

Calcium sulfate formed during the dissolution

reaction of colemanite with sulfuric acid crystal-
lizes as calcium sulfate dihydrate (Gypsum,
CaSO4  2H2O) in the reactor at the reaction
temperature. The gypsum crystals were separated
from the supernatant solution by suction filtration,
dried and examined under microscope. Fig. 4
shows the micrographs of the calcium sulfate
dihydrate crystals obtained from the dissolution of
colemanite in sulfuric acid at 801C and 200 rpm
with initial concentrations of [B2O3]o=0.777 and
[SO2

4 ]o=0.623 M at various stage of the process.
After the fast dissolution reaction of colemanite in
aqueous sulfuric acid, the nucleation of the
gypsum crystals first occurs from the supersatu-
rated solution and then the crystals grow on these
nuclei. The induction period, the time passed after
the formation of supersaturated solution until the
appearance of the nuclei, is quite short for the
formation of calcium sulfate dihydrate crystals
(less than a few minutes). Therefore, measurement
of the induction period could not be achieved.
Nevertheless, we could follow the growth of the
gypsum crystals under microscope by taking
samples at certain time after the dissolution of
colemanite in aqueous sulfuric acid. The first
sample taken in 3 min after the dissolution of
colemanite in aqueous sulfuric acid shows needle-
like crystals having average dimensions of 1 mm
width and 10–20 mm length (Fig. 4a). The crystals
become wider and taller on prolong crystallization Fig. 4. Light microscope images of the gypsum samples taken
as it can be seen from the images of the samples from the dissolution of colemanite in aqueous sulfuric acid at
taken at 30th, 60th and 90th minutes of crystal- 801C and a stirring rate of 200 rpm after (a) 3 min, (b) 30 min,
lization in Figs. 4b–4d, respectively. The gypsum (c) 60 min, (d) 90 min.
crystals grow up to 10 mm wide and 80 mm tall
within 90 min. Temperature and stirring rate do dissolution of colemanite in aqueous sulfuric acid
not have a significant effect on the size of gypsum at various temperatures and stirring rate but
crystals when comparing the micrographs of starting with the same initial concentrations of
gypsum samples taken at 270th minute after [SO2

4 ]o=0.623 and [B2O3]o=0.777 mol/l.
 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567 565

3.3. Crystallization kinetics

Recent studies have shown that the crystal

growth of calcium sulfate dihydrate on seed
crystals follows a second order kinetics from the
solution supersaturated in calcium and sulfate ions
[15,23,24,29]. The crystallization of gypsum from
the supersaturated solution obtained by dissolu-
tion of colemanite in aqueous sulfuric acid also
obeys a second order rate law which is expressed as
follows by assuming that the initial concentrations
of calcium and sulfate ions are equal:
d½Ca2þ 
rate ¼
¼ kð½Ca2þ 
½Ca2þ sat Þ2 ; ð2Þ
dt
where the crystal growth rate is given in
mol l
1 s
1, k is the rate constant in l mol
1 s
1 Fig. 5. Reciprocal concentration versus time plot for the
which is assumed to be constant during the growth crystallization of gypsum from the supersaturated solution
process and [Ca2+]sat is the saturation concentra- obtained by dissolution of colemanite in aqueous sulfuric acid
tion of the calcium ion in solution. at different temperatures (stirring rate is 200 rpm; initial
concentrations are [B2O3]o=0.777 and [SO2
4 ]o=0.623 mol/l).
Colemanite is almost completely dissolved in
aqueous sulfuric acid within the first few minutes
(t1 ) and about 90% of calcium sulfate gets
precipitated out in the form of calcium sulfate
dihydrate. If [Ca2+]sup is the supersaturation aqueous sulfuric acid at different temperatures
concentration of calcium ion at time t1 ; Eq. (2) (stirring rate is 200 rpm; initial concentrations are
can be integrated between t1 and t; as follows [B2O3]o=0.777 mol/l and [SO2
4 ]o=0.623 mol/l) as
1 shown in Fig. 5. This indicates that the crystal-
¼ kðt
t1 Þ
½Ca 
½Ca2þ sat
2þ lization of gypsum is a second order process. The
1 slope of the straight line gives the rate constant for
þ : ð3Þ the second order crystallization of gypsum at
½Ca sup
½Ca2þ sat
2þ
respective temperature. Table 2 gives the list of the
The reciprocal concentration of calcium ion kinetic data including the supersaturation concen-
versus time plot gives a straight line for the tration ([Ca2+]sup) obtained at time t1 after the
crystallization of gypsum from the supersaturated dissolution, saturation concentration ([Ca2+]sat),
solution obtained by dissolution of colemanite in the second order rate constant (k) for the crystal

Table 2
Kinetic data for the crystal growth of gypsum crystals from the supersaturated solution obtained by dissolution of colemanite in
aqueous sulfuric acid at various temperatures and at a stirring rate of 200 rpm starting with initial concentrations of [SO2

4 ]o=0.623
and [B2O3]o=0.777 mol/l. [Ca2+]sup: supersaturation concentration obtained within the first few minutes of dissolution, [Ca2+]sat:
saturation concentration, k: the rate constant for the second order crystal growth

Temperature (1C) [Ca2+]sat (mol l
1) [Ca2+]sup (mol l
1) k (L mol
1 s
1)

60 0.0052 0.0279 0.07870.003

70 0.0033 0.0240 0.10870.004
80 0.0031 0.0193 0.14670.006
90 0.0051 0.0351 0.21870.008
566 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567
Fig. 6. Arhenius plot for the crystallization of gypsum from the
supersaturated solution obtained by dissolution of colemanite
in aqueous sulfuric acid at different temperatures (stirring rate
is 200 rpm; initial concentrations are [B2O3]o=0.777 and
[SO2

4 ]o=0.623 mol/l).
growth of gypsum crystals from the supersaturated
solution obtained by dissolution of colemanite in
aqueous sulfuric acid at various temperature and a
stirring rate of 200 rpm starting with the initial
concentrations of [SO2
4 ]o=0.623 mol/l and
[B2O3]o=0.777 mol/l.
The evaluation of the kinetic data in an
Arhenius plot (Fig. 6) gives an activation energy
of 3472 kJ/mol for the crystal growth of gypsum
from the supersaturated solution obtained by
dissolution of colemanite in aqueous sulfuric acid.
This activation energy is smaller than the value
(14–15 kcal/mol) reported for the seeded crystal
growth of gypsum in salt free solutions at a
relatively lower temperature [15,24]. This differ-
ence may be attributed to the enhancement of the
crystal growth rate of gypsum by the presence of
boric acid and other impurities in the solution
obtained by dissolution of colemanite in aqueous
sulfuric acid.
Acknowledgements
Colemanite and sulphuric acid used in this study
were provided by Eti Holding A.S. , Financial
. s, A.S.
support to Mr. Çetin by Ozta , is gratefully
acknowledged. We also thank Ms. Kerime Guney .
for her assistance in chemical analysis.
References
[1] J.I. Kroschwitz, in: M. Howe-Grant (Ed.), Kirk-Othmer
Encyclopedia of Chemical Technology, Vol. 4, 4th Edition,
Wiley, New York, USA, 1992, p. 377.
[2] R. Will, Y. Sakuma, R. Willhalm, Boron minerals and
chemicals report, in: Chemical Economics Handbook,
SRI International, Menlo Park, CA, September. 1990,
p. 717.1000A.
[3] K.A.L.G. Watt, World Minerals and Metals’ No. 12,
British Sulphur Corp. Ltd., London, UK, 1973, pp. 5–12.
[4] C. Helvaci, R.J. Firman, Inst. Mining Metall Section B 85
(1976) 142.
.
[5] G. Ozbayo& glu, K. Poslu, Miner Proc. Extractive Metall.
Rev. 9 (1992) 245.
[6] J. Glater, J.L. York, K.S. Campbell, in: K.S. Spiegler,
A.D.K. Laird (Eds.), Principles of Desalinations, Aca-
demic Press, New York, 1980, p. 627.
[7] R.J. Hand, British Ceramic Trans. 96 (1997) 116.
[8] W.A. Deer, R.A. Howie, J. Zussman, in: An Introduction
to the rock-forming minerals, Second Edition, Longman,
London, 1992, pp. 612–619.
[9] A. Packter, J. Crystal Growth 21 (1974) 191.
[10] E. Badens, S. Veesler, R. Boistelle, J. Crystal Growth 198/
199 (1999) 704.
[11] J.P. Boisvert, M. Domenech, A. Foissy, J. Persello, J.C.
Mutin, J. Crystal Growth 220 (2000) 579.
[12] P.G. Klepetsanis, P.G. Koutsoukos, J. Crystal Growth 193
(1998) 156.
[13] P.G. Klepetsanis, P.G. Koutsoukos, J. Crystal Growth 98
(1989) 480.
[14] P.G. Klepetsanis, P.G. Koutsoukos, J. Colloid Interface
Sci. 143 (1991) 299.
[15] G.H. Nancollas, M.M. Reddy, F. Tsai, J. Crystal Growth
20 (1973) 125.
[16] S.T. Liu, G.H. Nancollas, J. Colloid Interface Sci. 52
(1975) 593.
[17] R.J. Meyer (Ed.), Gmelin’s Handbuch der Anorganischen
Chemie, Calcium, Tlb-Lfg 3, Syst.-Nummer 28, Verlag
Chemie, Berlin, 1961.
.
[18] M. Broul, J. Nivlt, O. Sohnel, Elsevier Scientific Pub.
Comp. 149 (1981) 150.
[19] W.F. Linke, D. Van Nostrand Company Inc. 1 (1958)
660.
[20] G.H. Nancollas, A.E. Eralp, J.S. Gill, Soc. Pet. Eng. J. 18
(1978) 133.
[21] P.G. Klepetsanis, E. Dalas, P.G. Koutsoukos, Langmuir
15 (1999) 1534.
[22] N. Yavaso&, glu-Taylan, H. Gurb
. uz,
. O. . Ozcan,
. P. Sayan, G.
. A.N. Bulutcu,
Gur, , Proceedings of UKMK-3, Erzurum,
1998, 1084.
[23] J.S. Gill, G.H. Nancollas, J. Crystal Growth 48 (1980) 34.
[24] B.R. Smith, F. Sweett, J. Colloid Interface Sci. 37 (1971)
612.
.
[25] M. Oner, . Do&gan, G. Oner,
O. . J. Crystal Growth 186
(1998) 427.
 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567 567

[26] C. Rinaudo, A.M. Lanfranco, R. Boistelle, J. Crystal
Growth 158 (1996) 316.
[27] Z. Amjad, Can. J. Chem. 66 (1988) 1529.
[28] B.R. Smith, A.E. Alexander, J. Colloid Interface Sci. 34
(1970) 81.
[29] W.P. Brandse, G.M. van Rosmalen, G. Brouwer, J. Inorg.
Nucl. Chem. 39 (1977) 2007.
[30] M.R. Christoffersen, J. Christoffersen, M.P.C. Weijnen,
G.M. van Rosmalen, J. Crystal Growth 58 (1982)
585.
[31] A. Balkan, R. Tolun, Bull. Tech. Univ. Istanbul 38 (1985)
207.
[32] J.G. Anderson, M.A. Larson, L.K. Doraiswamy, Chem.
Eng. Science 53 (1998) 2459–2468.