1534

Langmuir 1999, 15, 1534-1540

Role of Temperature in the Spontaneous Precipitation of

Calcium Sulfate Dihydrate
Pavlos G. Klepetsanis, Evangelos Dalas, and Petros G. Koutsoukos*,
Department of Pharmacy, University of Patras, University Campus, GR 265 00 Patras, Greece,
Department of Chemistry, University of Patras, University Campus, GR 265 00 Patras, Greece,
and Institute of Chemical Engineering and High Temperature Chemical Processes and
Department of Chemical Engineering, University of Patras, University Campus,
GR 265 00 Patras, Greece
Received January 23, 1998. In Final Form: November 5, 1998
The spontaneous precipitation of calcium sulfate in supersaturated solutions over the temperature
range between 25.0 and 80.0 C was investigated by monitoring the solution specific conductivity during
desupersaturation. From measurements of the induction times preceding the onset of precipitation the
surface energy of the forming solid, identifield as gypsum, was found between ca. 12 and 25 mJ m-2 for
the temperature range between 80.0 and 25.0 C, respectively. Kinetics analysis showed that over 50 C
it is possible that anhydrous calcium sulfate is forming as a transient phase converting into the more stable
calcium sulfate dihydrate. The linear dependence of the rates of precipitation on the relative solution
supersaturation suggested a mechanism according to which the growth units are integrated into the active
sites of the supercritical nuclei by surface diffusion. According to the morphological examination of the
crystals it is possible that crystal growth occurs by the advancement of steps.

Introduction
The formation of calcium sulfate scales is a welldocumented phenomenon encountered in a wide spectrum
of industrial processes and applications including oil
production by water-flooding, in particular for cases where
incompatible waters are used,1 desalination of seawater
by reverse osmosis,2 handling of geothermal brines for
energy production,3 water distillation,4 phosphoric acid
production by acidification of phosphorites with sulfuric
acid,5 etc. Despite the fact that the system has been
intensively investigated over the past three decades many
aspects await reliable answers. A considerable amount of
the published literature is concerned with batch, seeded
growth studies,6-12 investigations in various hydrodynamic conditions,11-13 and spontaneous precipitation
experiments.14-16 The solution chemistry of the aqueous

Department of Pharmacy.
Department of Chemistry.
Institute of Chemical Engineering and High Temperature
Chemical Processes and Department of Chemical Engineering.

(1) Cowan, J. C.; Weintritt, D. J. Water Formed Scale Deposits; Gulf

Publ. Co.: Houston, TX, 1976; p 60.
(2) Tsuge, H.; Sugino, Y.; Takeda, M.; Matsumura, T. Proceedings
of the 9th Annual NSWIA Conference; Washington, DC, 1981.
(3) Weismantel, G. Chem. Eng. 1973, 80, 40.
(4) BETZ Handbook of Industrial Water Conditioning, 8th ed.; Betz
Lab. Inc.: Trevose PA, 1982; pp 202-204.
(5) Glater, J.; York, J. L.; Campbell, K. S. In Principles of Desalination;
Spiegler K. S., Laird A. D. K., Eds.; Academic Press: New York, 1980;
p 627.
(6) Liu, S. T.; Nancollas, G. H. J. Cryst. Growth 1970, 6, 282.
(7) Nancollas, G. H. Adv. Colloid Interface Sci. 1979, 10, 215.
(8) Nancollas, G. H.; White, W.; Tsai, F.; Maslow, L. Corrosion 1979,
35, 304.
(9) van Rosmalen, G. M.; Daudey, P. J.; Marchee, W. G. J. J. Cryst.
Growth 1981, 52, 801.
(10) Gardner, G. L. J. Phys. Chem. 1978, 82, 864.
(11) Meijer, J. A.; van Rosmalen, G. M. Desalination 1980, 34, 217.
(12) Amjad, Z.; Hooley, K. J. Colloid Interface Sci. 1986, 111, 496.
(13) Hasson, D.; Zahavi, J. Ind. Eng. Chem. Fundam. 1970, 9, 1.
(14) Klepetsanis, P. G.; Koutsoukos, P. G. J. Cryst. Growth 1989, 98,
480.
(15) Macek, J.; Zakarejsek S.; Radkovic, J.; Bole V. J. Cryst. Growth
1993, 132, 99.
(16) Sohnel, O.; Haldirova, M. Cryst. Res. Technol. 1984, 19, 477.

media in which the various calcium sulfate hydrates form

is very important and needs to be carefully considered in
order to quantify the mechanisms of the formation of the
various calcium sulfate forms. Calcium sulfate may
crystallize as gypsum (CaSO42H2O, CSD), calcium sulfate
hemihydrate (CaSO41/2H2O, CSH) and anhydrite (CaSO4,
CSA). The solubility of all calcium sulfate forms decreases
with increasing temperature, a fact that is responsible
for the formation of calcium sulfate scale on heat exchanger
surfaces. The precipitation process includes both nucleation and crystal growth steps which are mechanistically
different. The kinetics analysis is often complicated when
the precipitation process is investigated under rapidly
changing solution conditions. In the majority of the
published work the key variable, the solution supersaturation, is rapidly changing especially during the initial
stages of the precipitation of calcium sulfate. The operation
of primary and secondary nucleation and crystal growth
in the same experiment may complicate the interpretation
of the results.
In the present work we have monitored carefully the
solution desupersaturation during the formation of calcium sulfate over a wide solution temperature range. Since
the formation of this salt is not pH dependent,14 monitoring
of the solution supersaturation was effected by measuring
the specific conductance throughout the precipitation
process. The kinetics results from the batch experiments
done under carefully controlled conditions of temperature
and solution supersaturation have been analyzed in an
attempt to deduce the prevalent mechanism in the
formation of calcium sulfate. The experimental temperatures were extended in regions (up to 80 C) in which
calcium sulfate forms other than CSD may form.
Experimental Section
The experiments reported in the present work were batch type,
done in a glass reactor, volume totaling 0.600 dm3. The
homogeneity of the solution with respect to all chemical
components was ensured by magnetic stirring of the solutions
at about 400 rpm. The temperature control (( 0.1 C) was effected

10.1021/la9800912 CCC: $18.00 1999 American Chemical Society

Published on Web 01/21/1999

Precipitation of Calcium Sulfate Dihydrate

Langmuir, Vol. 15, No. 4, 1999 1535

Figure 1. Schematic of the electronic circuitry of the electronic amplifier used for the measurement of very small changes of the
solution specific conductivity. The symbols correspond to the electronic parts as follows: IC1,2,3, LM308; IC4, LM741H; R1 ) 100
k, 1%; R2, R3 ) 50 k, 1%; R4 ) R5 ) R6 ) R7 ) 4 k, 1%; R8 ) R9 ) 100 , 1%; R10 ) 100 k, 1%; RF ) 100 , 1%; VR1 )
10 k; VR2 ) 50 k; C1 ) C2 ) 100 pF, 5%; C3 ) C4 ) C5 ) 1 nF, 5%; power supply (12 V.
by circulating water from a thermostat through a jacket
surrounding the reactor. Stock solutions of calcium nitrate and
ammonium sulfate were prepared from the corresponding
crystalline solids (Merck Puriss) using triply distilled water. The
solutions, prior to their standardization, were filtered through
membrane filters (0.2 m, Millipore, Bedford, MA). The calcium
stock solutions were standardized with photometric titrations
with standard EDTA solutions (Merck, Titrisol) using murexide
indicator and by atomic absorption spectrometry (Varian 1200).
Ammonium sulfate stock solutions were standardized by titration
with standard barium chloride solutions (Merck, Titrisol) and
by ion chromatography (Metrohm IC 690).
The supersaturated solutions were prepared directly in the
thermostated reactor by simultaneously mixing equal volumes
(0.250 dm3 each) of the calcium nitrate and ammonium sulfate
solutions, through a Y-shaped glass tube. The mixing was done
in less than 20 s, and maximum reproducibility was thus achieved.
Immediately following mixing of the reagents and the establishment of the supersaturation the reactor was sealed with a Perspex
lid bearing holes for the accommodation of a conductivity cell
(Radiometer PP1042) and for sampling. The solution specific
conductivity was measured with a conductivity meter (Radiometer, CDM 3). To enhance the output signal of the conductivity
meter and be able consequently to measure changes in the
solution specific conductivity as small as 1 S cm-1, a special,
low-cost amplifier was designed, and the corresponding electronic
circuit is shown in Figure 1. A calibration line was made by
measuring the specific conductivity and its relative differences
in solutions titrated with standard calcium nitrate solutions both
in the presence and in the absence of ammonium sulfate in order
to avoid errors due to ion pair formation. Through linear
regression of the calibration data, equations relating solution
conductivity to solution concentration were established for all
temperatures in which experiments were done.17,18 A typical
(17) Smith, B. R.; Sweet, F. J. Coll. Interface Sci. 1971, 37, 612.
(18) Christoffersen, M. R.; Christoffersen, J.; Weijnen, M. P. C.; van
Rosmalen, G. M. J. Cryst. Growth 1982, 58, 585.

Figure 2. Calibration curve for the correlation of the specific

conductivity of the supersaturated solutions with the concentration of calcium in solution. (For each calibration point
equimolar (total calcium):(total Sulfate) ) 1:1 solutions were
used; 25 C.)
calibration curve is shown in Figure 2. The variation of the specific
conductivity of the solution concomitant with the desupersaturation in a typical spontaneous precipitation experiment and
the corresponding calcium concentration are also shown in the
same figure. The time lapsed between the establishment of the
solution supersaturation and the measurement of the first
changes of the specific conductivity measured was defined as the
induction time, , preceding the spontaneous precipitation of
calcium sulfate. The precise determination of the induction time
was done by the determination of the inflection point of the specific
conductivity-time curve, plotting the derivative of the specific
conductivity variation with time. In preliminary experiments it
was established that the conductivity probe did not induce the
precipitation of calcium sulfate. In these experiments, the

1536 Langmuir, Vol. 15, No. 4, 1999

Klepetsanis et al.
Table 1. Equilibria Involved in the
CaCl2-(NH4)2SO4-H2O System and the Corresponding
Stability Constantsa
equilibrium

log K25
(I f 0)

HSO4- ) H+ + SO42CaSO40 ) Ca2+ + SO42NH4SO4- ) NH4+ + SO42CaNO3+ ) Ca2+ + NO3H2O ) H+ + OHNH4+ ) H+ + NH3
CaSO42H2O(s) ) Ca2+ + SO42- + 2H2O

1.99
2.31
1.11
0.06
13.99
9.24
-4.62

H
(kcal/mol)
5.4
1.6
-6.0
-13.34
-12.45
0.3

a Martell, A. E.; Smith, R. M. Critical Stability Constants; Plenum

Press: New York, 1981; Vol. 4.

Figure 3. Variation of the solution specific conductance (O)

and of the number of particles (b) with time for the spontaneous
precipitation of calcium sulfate in supersaturated solution
(experiment no. 101).
precipitation process was monitored turbidimetrically measuring
light transmission. Moreover, in all experiments reported in the
present work the total amount of crystals formed up to the end
of each run did not affect the solution specific conductance
measured.14 The rates reported were computed at the point of
maximum slope of the conductivity-time plots for each experiment. The number of particles was found to reach a constant
value, suggesting that, at this point, the number of active centers
for crystal growth was constant. Typical plots, showing the
constancy of the particle number as a function of the variation
of the solution specific conductance during the spontaneous
precipitation of calcium sulfate, are shown in Figure 3. During
the course of precipitation samples were withdrawn for the
measurements of the number and of the size distribution of the
precipitating particles as well as for the verification of the validity
of the calibration curve used for the measurement of calcium
concentration in solution. Knowledge of the total calcium
concentration and of the stoichiometry of the precipitating salt
(Ca:SO4 ) 1:1) allowed for the calculation of the solution
supersaturation with time during the precipitation process. The
number and the particle size distributions were measured by a
rotating laser scattering counter (Spectrex ILI 1000) connected
with a computer for the data acquisition and subsequent analysis.
Calcium analyses were done by ion chromatography and/or by
spectrophotometric titrations. The solid phases were collected
at the end of the precipitation process by filtration through
membrane filters. Following drying at 40 C overnight the solids
were characterized by powder X-ray diffraction (Philips 1840/
00) scanning electron microscopy (SEM, JEOL JSM 5200),
infrared spectrometry (Perkin-Elmer 1760 FTIR), thermogravimetic analyses (DuPont 910), and specific surface area (SSA)
measurements by a multiple point dynamic BET method.

Results and Discussion

In all experiments and over the temperature range (2580 C) investigated in the present work CSD was the only
calcium sulfate phase found, although thermodynamic
calculations would predict the formation of CSA over
temperatures exceeding 50 C.13 It should be noted
however that the phase identification was done following
filtration of the aqueous media at room temperature, a
fact which may have contributed decisively to the conversion of CSA eventually formed at the inital precipitation
stages into CSD by hydration. The chemical nature of the
solid precipitate was identified further by powder X-ray
diffraction19 and infrared spectroscopy.20 TGA analyses
of the precipitates yielded a weight loss of 20.9%, corresponding to CSD.19 The driving force for the formation of
(19) Klepetsanis, P. G.; Koutsoukos, P. G. J.Colloid Interface Science,
1991, 143, 299.
(20) Zussman, J. In Physical Methods in Determinative Mineralogy;
Academic Press: London, 1977.

calcium sulfate dihydrate is the change in the Gibbs free

energy G for going from the supersaturated solution to
equilibrium. The average per ion energy is given by

G ) -

2+
2RT (Ca )(SO4 )
ln
2
K0sp

(1)

where ( ) denote activities, R and T are the gas constant

and the absolute temperature, respectively, and K0sp is the
thermodynamic solubility product of CSD. The ratio

(Ca2+)(SO42-)
K0sp

(2)

is the supersaturation ratio. The (relative) supersaturation

is defined as

) 1/2 - 1

(3)

It is obvious that the calculation of the solution

supersaturation with respect to any calcium sulfate
hydrate requires knowledge of the activities of all ions
involved. The distribution and the activities of the ionic
species in the supersaturated solutions were computed
by taking into consideration the equilibria and the
respective constants summarized in Table 1. In cases in
which data for the thermodynamic constants were not
available for all temperatures the constants were computed using enthalpies of formation. In addition to the
equilibria shown in Table 1, the mass balance equations
for total calcium, Cat, and total sulfate, St, along with the
electroneutrality conditions were used and successive
iterations were made for the ionic strength.21 The activity
coefficients of the z-valent ions, z were calculated from
an extended Debye-Huckel equation22

log z ) -

Az2I1/2
+ bI
1 + BaI1/2

(4)

where I is the solution ionic strength, A and B are the

Debye-Huckel constants,23 and a and b are constants
characteristic for each ionic species. Values of a and b are
summarized in Table 2. The temperature dependence of
the equilibrium constants was taken into consideration
for the calculations at temperatures other than 25 C,
using the enthalpy values and the vant Hoff equation.
For the solubility products of CSD and CSA the expression
(21) Nancollas, G. H. Interactions in Electrolyte Solutions; Elsevier:
Amsterdam, 1966; p 115.
(22) Ball, J. W.; Nordstrom D. K. WATEQ 4F-Program for Calculation
of Species Concentration in Seawater; USGS: Washington, DC, 1987.
(23) Robinson, R. A.; Stokes, R. H. Electrolyte Solutions; Butterworths: London, 1959; p 145.

Precipitation of Calcium Sulfate Dihydrate

Langmuir, Vol. 15, No. 4, 1999 1537

Table 2. Values for the Coefficients a and b (Eq 4) for

the Species in the Ca(NO3)2-(NH4)2SO4 System
ionic species

ionic species

Ca2+
SO42-

5.0
5.0

0.165
-0.040

NH4+
NH4SO4-

2.5
5.4

0.000
0.000

Table 4. Coefficients for the Calculation of the Solubility

Product of Calcium Sulfate as a Function of
Temperature
solid

A1

A2

10-6A3

A4

A5

CSD
CSA

182.532
164.814

-0.48932
-0.46478

-10.325
-10.764

-67441.7
-68807. 8

1156.21
1059.51

Table 3. Initial Conditions, Supersaturation, Induction

Times, and Initial Rates for the Spontaneous
Precipitation of Calcium Sulfate Dihydrate at Various
Temperatures (Total Calcium, Cat ) Total Sulfate, St)
expt
no.

102Cat
(M)

(C)

(min)

G
(kJmol-1)

10-5R
(Mmin-1)

101
102
103
104
105
106
111
112
113
114
115
121
122
123
124
131
132
133
134
135
141
142
143
144

5.0
4.75
4.25
4.0
3.75
3.5
3.4
3.3
3.2
3.1
3.0
3.2
3.0
2.80
2.75
2.5
2.4
2.3
2.25
2.1
2.35
2.25
2.1
2.0

25.0
25.0
25.0
25.0
25.0
25.0
38.4
38.4
38.4
38.4
38.4
50.0
50.0
50.0
50.0
65.0
65.0
65.0
65.0
65.0
80.0
80.0
80.0
80.0

32
39
45
52
89
105
26
24
54
81
106
11
35
49
95
8
21
29
42
163
14
16
37
204

-1.55
-1.47
-1.31
-1.22
-1.13
-1.02
-0.98
-0.94
-0.89
-0.84
-0.79
-0.95
-0.84
-0.74
-0.71
-0.70
-0.63
-0.56
-0.52
-0.41
-0.82
-0.75
-0.63
-0.54

6.8
5.9
2.1
1.9
1.0
0.5
6.0
5.1
4.5
2.4
2.1
2.0
1.2
0.9
0.7
2.4
1.9
1.7
1.3
0.8
12.1
7.2
2.0
1.3

Figure 4. Experimental conditions (Table 3, represented by

rectangles) and the solubility isotherms of the three calcium
sulfate hydrates: plot of solubility as a function of temperature.

of eq 5 was used for the calculation of the respective

ln K0s )

A2T
A3
A5
A1
A4
ln T +
+
+
2
R
2R
RT
R
2RT

(5)

solubility products at various temperatures.24 The values

for the constants Ai (i ) 1-5) are given in Table 4. The
spontaneous precipitation of CSD was preceded by induction times which were inversely proportional to the
solution supersaturation. The experimental conditions and
the kinetics results obtained are summarized in Table 3.
In general, the conditions of the working solutions were
below the solubility isotherm of CSH with the exception
of part of the set of experiments done at 80 C, as shown
in Figure 4. The dependence of the induction periods
measured for various supersaturations and temperatures
are shown in Figure 5. From the experimental methodology employed, it is obvious that the induction times, ,
measured include both the time needed for nucleation, n,
and the time, g, required for the critical nucleus to grow
to a size which would correspond to the extent of ion
depletion needed by the conductivity probe to give an
appropriate change in the specific conductance of the
supersaturated solution,25 i.e.

) n + g

(6)

The strong dependence of the induction times on the

solution supersaturation which was more pronounced at
(24) Krishnam, R. U. G.; G. Atkinson, J. Chem. Eng. Data 1990, 35,
361.
(25) Mullin, J. W. Crystallization, 2nd ed.; Butterworth-Heinemann: Oxford, U.K., 1992.

Figure 5. Plot of the induction times preceding the spontaneous

precipitation of calcium sulfate dihydrate as a function of
temperature and the solution supersaturation.

higher temperatures should be ascribed to the sensitivity

of nucleation on both supersaturation and temperature.
The dependence of the induction time on temperature
and the solution supersaturation, assuming steady state,
is given by eq 7, where C1 and C2 are constants. Constant

log )

C1
3

T log2

- C2

(7)

C1 is given by eq 8 as a function of the shape of the C,

C1 )

s32
(2.303k)32

(8)

forming nuclei, the molecular volume, , and the surface

energy, s, of the solid phase forming, where is a shape
factor (taken as 16/3 here, assuming spherical shape for
the nuclei forming), k is Boltzmanns constant, and is

1538 Langmuir, Vol. 15, No. 4, 1999

Figure 6. Plots of the induction times measured at various

temperatures as a function of the inverse of the square of the
logarithm of the relative supersaturation: (O) 25 C; (9) 38 C;
([) 50 C; (4) 65 C; () 80 C.

Figure 7. Variation of surface energies determined from

nucleation kinetics data as a function of temeperature: (O)
data from ref 28; (9) present work.

the number of ions in the calcium sulfate crystals ( ) 2).

Plots according to eq 7 are shown in Figure 6. As may be
seen, at all temperatures except for 65 C, a single straight
line was obtained for each set of experiments. At 65 C the
plot consisted of two linear parts with a change in the
slope at about )1.51. The steeper part may be ascribed
to homogeneous precipitation while the other part to
primarily heterogeneous.26,27 From the slopes of the
straight lines, the surface energies were computed for each
temperature, and as may be seen in Figure 7, their values
are in good agreement with literature values obtained
from measurements of rates of precipitation and of
induction times from calcium sulfate nucleation experiments,28,29 while the extension of the temperature range
to 80 C showed a decrease of the surface energies with
temperature as expected.30
In our experiments, variation of the stirrer speeds
between 100 and 400 rpm did not show any effect in the
measured rates of CSD precipitation suggesting that the
process was not mass transport controlled. Moreover, if
mass transport were the rate-determining mechanism for
(26) Sohnel, O.; Mullin, J. W.; Jones, A. G. Ind. Eng. Chem. Res.
1988, 27, 1721.
(27) Sohnel, O.; Garside, J. Precipitation; Butterworth-Heinemann:
Oxford, U.K., 1992; pp 66-70.
(28) Keller, D. M.; Massey, R. E.; Hileman, O. E., Jr. Can. J. Chem.
1978, 56, 831.
(29) Linnikov, O. O. Russ. J. Appl. Chem. 1995, 68, 1023.
(30) Adamson, A. W. Physical Chemistry of Surfaces, 5th ed.; J.
Wiley: New York, 1995.

Klepetsanis et al.

Figure 8. Plot of the rate of calcium sulfate precipitation, RP,

as a function of the solution supersaturation, : (b) 25.0 C;
(O) 38.5 C; ( ) 50.0 C; (4) 65.0 C; () 80 C.

Figure 9. Typical powder X-ray diffraction spectrum of calcium

sulfate dihydrate obtained by spontaneous precipitation

Figure 10. Plot of the logarithm of the rate constants

determined from the kinetics of precipitation of calcium sulfate
over the temperature range between 25 and 80.0 C as a function
of the inverse of the absolute temperature.

the formation of CSD, the overall rate measured should

be

rate RP )

DvC

(9)

where Dv is the diffusion coefficient (ca. 1 10-9 m2 s-1),

C is the CSD solubility (4.9 10-3 mol dm-3), and is
the diffusion layer thickness. The rates measured at the
corresponding supersaturations (Table 3) would correspond to diffusion layer thickness values about 10 mm
(assuming a specific surface area for the growing crystals
of 1 m2 g-1, value measured at the end of the crystallization

Precipitation of Calcium Sulfate Dihydrate

Langmuir, Vol. 15, No. 4, 1999 1539

Figure 11. Scanning electron micrographs of gypsum crystals precipitated spontaneously in aqueous supersaturated solution:
(a) 25 C; (b) 65 C; (c-f) 80 C.

experiments). This value is unrealistic, supporting further

a surface diffusion controlled mechanism.31 According to
this mechanism the rate-determining step is the integration of the growth units in the active sites of the growing
supercritical nuclei. For aqueous solutions the overall rate,
RP, depends linearly on the solution supersaturation:32

RP ) kP

(10)

Here kP is the rate constant. Plots according to eq 10 are

shown in Figure 8. It should be noted that the kinetics
analysis was done on the basis of the mineral phase found
after the collection of the precipitate from the reactor which
in all cases was identified as CSD. Typical powder X-ray
diffractogram obtained from precipitates is shown in
Figure 9. From the kinetics plot it may be seen that a
discontinuity was found for the apparent rate constant
between temperatures 38.5 and 50.0 C. From the
solubility isotherms of the calcium sulfate system shown
in Figure 4, it may be seen that at this temperature CSA
(31) Liu, Y.; Nancollas, G. H. J. Cryst. Growth 1996, 165, 116.
(32) Bennema, P. J. Crystal Growth 1967, 1, 278.

is more stable. Since the rate constants (represented by

the slopes of the straight lines) for the kinetics of
precipitation measured increased from 25.0 to 38.5 C
and again from 50.0 to 80.0 C, it may be concluded that
a different mineral, CSA, precipitates at these temperatures. That this intermediate phase was not identified
is probably due to the fact that the analysis by XRD was
done following drying at room temperature at which
conversion to the more stable CSD is very likely. It should
be noticed that CSH may convert into CSD in the solid
state in the presence of air humidity alone.33 The variation
of the apparent rate constants with temperature is shown
in Figure 10. With application of an Arrhenius formalism,
two values were calculated for the respective activation
energies of the mineral phases precipitating: 46 and 67
kJ mol-1. Both values should be considered rather as
temperature coefficients, but their magnitudes corroborated further the surface diffusion controlled mechanism
for the spontaneous formation of the mineral phase in
(33) Semenovich, I. S. Kinetics of Phase Transitions of Calcium
Sulfate Hydrates under Conditions of Phosphoric Acid Wet Process
Production. Ph.D. Thesis, Research Institute of Fertilizers and Insectofungicides (NIUI F NPO Minudobreniya), Moscow, 1992.

1540 Langmuir, Vol. 15, No. 4, 1999

supersaturated calcium sulfate solutions over the temperature range between 25.0 and 80.0 C. Both values are
in very good agreement with activation energies reported
in the literature for the precipitation in brines34 and in
synthetic supersaturated solutions.6,17
The first-order dependence of the measured rates of
precipitation on the relative supersaturation is consistent
with the prediction of the Burton, Cabrera, and Frank
spiral growth theory35 a mechanism inferred by Christoffersen.18 Further studies however involving the use of
scanning force microscopy failed to verify the observation
of spirals in calcium sulfate dihydrate crystals, even at
very low supersaturations, and it was shown that the
growth takes place by the advancement of elementary
steps.36,37 Examination of the morphology of the precipitated gypsum crystals by SEM showed the formation of
characteristic prismatic habits shown in Figure 11. The
(34) Kushnir, J. Geochim. Cosmochim. Acta 1980, 44, 1471.
(35) Burton, W. K.; Cabrera, N.; Frank, F. C. Philos. Trans. R. Soc.
London 1951, A243, 299.
(36) Bosbach, D.; Rammensee, W. Geochim. Cosmochim. Acta 1994,
58, 843.
(37) Hall, C.; Cullen, D. C. AIChE J. 1996, 42, 232.

Klepetsanis et al.

edge of the crystals, as may be seen in the micrograph

Figure 11e consisted of layers. On the surface of the top
layer, advancing steps could be noticed (Figure 11f) thus
supporting the previous reports concerning crystal growth
of gypsum by advancing steps.
In conclusion, the spontaneous precipitation of calcium
sulfate dihydrate over the temperature range between
25.0 and 80.0 C was found to be a surface diffusion
controlled process in which the rates of precipitation varied
linearly with the solution supersaturation. The estimate
of the apparent activation energy supported further this
conclusion. The measurements were done by monitoring
the changes of the specific conductivity of the supersaturated solutions during the solid formation process. From
the kinetics data and particularly from the dependence
of the induction times preceding the onset of precipitation
on the solution supersaturation, the surface energies of
the solid phases forming were of the order of magnitude
anticipated for sparingly soluble salts and they decreased
with increasing temperature.
LA9800912