Chemical Engineering Science 56 (2001) 53915400

www.elsevier.com/locate/ces

Thermodynamics and kinetics for mixed calcium carbonate and

calcium sulfate precipitation
T. H. Chong, R. Sheikholeslami
School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, 2052, Australia
Received 30 August 2000; received in revised form 23 May 2001; accepted 25 May 2001

Abstract

The e/ects of CaSO4 on CaCO3 precipitation were studied in the batch tests at 60, 70 and 80 C in mixtures having calcium carbonate as the dominant salt and at a given total initial calcium concentration of 0:03 M with sulfate concentration ranging from 0 to
0:01 M. Solubility products and rate constants were determined from thermodynamic and kinetic studies and the results indicated that
even minute amounts of calcium sulfate a/ect the thermodynamics, kinetics and the scale structure and no longer the solubility data
and rate constants for the pure salt were applicable. Presence of CaSO4 from 0.002 to 0:01 M increased the calcium carbonate solubility product more than an order of magnitude. The e/ect of salt mixture on the solubility constant of non-dominant salt (calcium sulfate) was reverse as calcium sulfate solubility increased to its pure value with increases in its molar ratio. In addition, the rate equation
suggested in the literature (Nancollas and Reddy, J. Colloid Interface Sci. 37 (1971) 824; Reddy and Nancollas, J. Colloid Interface
Sci. 36 (1971) 166) for pure salt was not applicable to the experimental data. The general observations indicated that the presence
of CaSO4 had weakened the CaCO3 scale which is usually very adherent. The experimental results did take into account the e/ect
of solution ionic strength, however, they suggest that data for pure salt precipitation seem not to be extendable to co-precipitation.
? 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Fouling; Precipitation; Co-precipitation; Calcium sulfate; Calcium carbonate; Composite fouling; Thermodynamics; Kinetics

1. Introduction
Fouling is the accumulation of undesired solid materials at the phase interfaces. Build-up of fouling =lm leads
to an increase in resistance and deteriorates the performance of process equipment such as membranes and heat
exchangers and is costing industries billions of dollars
annually. One of the major fouling phenomena encountered in the aqueous systems is scale formation due to
precipitation of salts present in the water. Lots of metals and anions exist naturally in the water; among them,
CaCO3 and CaSO4 are major fouling contributors. Both
these salts have inverse solubility behaviour where the
solubility decreases with increasing temperature and salts

Corresponding author. Tel.: +61-2-9385-4343; fax: +61-29385-5966.

E-mail address: r.sheikholeslami@unsw.edu.au
(R. Sheikholeslami).

precipitate on heat exchange surfaces when the solution

becomes supersaturated.
Crystallization has been studied for many years as
shown in the two monographs by Mullin (1972, 1993).
An immense body of information is available on thermodynamics and kinetics of crystallization of calcium carbonate (Augustin & Bohnet, 1995; Nancollas & Reddy,
1971; Plummer & Busenberg, 1982) and calcium sulfate
(Liu & Nancollas, 1970; Nancollas, Eralp, & Gill, 1978;
Zhang & Nancollas, 1992). The research in the area of
crystallization fouling, including the dynamic e/ects, has
also been extensive as covered in two comprehensive reviews (Hasson, 1981, 1999). However, due to the complexity of fouling process the research in this area usually
involves fouling by a single precipitant. The area to which
not much attention has been paid to is the interactive
e/ect of co-precipitating salts with or without common
ions. These include solubility e/ects, rate data, crystal
structure and strength, inhibitor e/ects and also dynamic

0009-2509/01/$ - see front matter ? 2001 Elsevier Science Ltd. All rights reserved.
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T. H. Chong, R. Sheikholeslami / Chemical Engineering Science 56 (2001) 53915400

e/ects. This is important for two reasons. One is that the

mechanism of fouling might be di/erent for di/erent salts
as it was shown to be di/erent for CaCO3 and CaSO4
(Bansal, Muller-Steinhagen, & Chen, 1997). The second
is the fact that co-existence of salts might actually a/ect
the thermodynamic and kinetic behaviour of each salt and
therefore, the single salt data might not be applicable to
the condition when the salts co-exist. The reviewed literatures on crystallization (Hasson, 1981, 1999) indicate
that very little study has been devoted to the study of
the co-precipitation phenomenon. There has been some
qualitative research (Bramson, Hasson, & Semiat, 1996;
Hasson & Karmon, 1984) on the strength and tenacity
of co-precipitated calcium carbonate and sulfate. They
found that a major factor a/ecting scale tenacity was the
purity of the deposit. For calcium sulfate, the higher the
impurities, the greater the strength of the scale; however,
with calcium carbonate, adhesive strength was seen to decrease with increasing impurities. The most diGcult deposit to remove from heat transfer surfaces was calcium
carbonate scale with impurities measuring less than 5%
by mass; pure calcium sulfate deposits were found to be
far less adherent than deposits containing co-precipitated
calcium carbonate. The co-precipitated calcium carbonate seems to act as bonding cement, enhancing considerably the strength of calcium sulfate scale layer. In an
earlier study, Morse and Knudsen (1977) also reported
that for aggressive scale, the main constituent was calcium carbonate.
In our recent work (Sudmalis & Sheikholeslami,
2000) on co-precipitation of CaCO3 and CaSO4 when
they exist in comparable ratios, it has been qualitatively shown that co-precipitation a/ects thermodynamics and kinetics of precipitation as well as the scale
structure. The objective of this study is to investigate and quantify co-precipitation process of CaCO3
and CaSO4 when CaCO3 is the predominant component at a constant total calcium concentration and
to determine solubility constants, assess the reaction
rate constants and therefore examine the applicability of data and mechanisms for pure precipitation to
co-precipitation.
2. Background
Understanding and developing kinetic and rate correlations and models for co-precipitation are built
on the theories of single salt precipitation and hence
crystallization theory and properties of CaCO3 and
CaSO4 are brieJy discussed here. In general, crystallization is considered to be comprised of nucleation,
growth and re-crystallization steps. There are various
mechanisms for each step and a great degree of overlap among these steps (Sudmalis & Sheikholeslami,
2000). For crystallization to occur the solution has

to be supersaturated; however, supersaturation by itself is not suGcient to induce crystallization. There

is a requirement for centers of crystallization that can
take various forms such as seeds, embryos or foreign
matter present in the solution to induce nucleation.
Growth and re-crystallization follow the nucleation
step. Usually, nucleation is the controlling step; once
the critical nuclei are formed, the crystallization
proceeds.
A given salt may have di/erent crystal structures
of which some might be more stable or more readily
formed. Calcium carbonate occurs naturally in three crystal structures of calcite, aragonite and vaterite. Calcite is
the most stable form of calcium carbonate. The aragonite polymorph is metastable and irreversibly changes to

calcite when heated in dry air to about 400 C. Vaterite

is metastable and least prevalent and transforms to calcite and aragonite under geological conditions (Reeder,
1990). The crystal forms of calcite are hexagonal whereas
aragonite is in the orthorhombic system. Physical properties of the two more prevalent crystal polymorphs
are given by Lepley (1984); corresponding values for
vaterite are not available. The solubility product for
calcium carbonate and the dissociation constants for
carbonic acids are given by Bott (1995). Saturation solubility of calcium carbonate depends on the CO2 content
and solution pH; Kemmer (1988) provides data showing the distribution of CO2 related ions and CO2 gas in
solution as a function of pH.
Calcium sulfate can exist in six di/erent solid phases
(3 anhydrites, 2 hemihydrates and a dihydrate). Gypsum (CaSO4 :2H2 O), hemihydrates (CaSO4 :1=2H2 O),
and anhydrite III and anhydrite II can exist at room tem
peratures whereas anhydrite I only exists above 1180 C.
The physical properties of all polymorphs are given by
Wirsching and Gipswerke (1985). Much research has
been performed in an attempt to analyse the mechanism
and determine the form of calcium sulfate at di/erent
temperatures. Partridge and White (1929) found that
gypsum is the usual precipitating phase in the range

of 40 98 C while anhydrite and hemihydrate are the

species likely to precipitate above 98 C. Some others

(Blount & Dickson, 1973; Hardie, 1967) indicated the
transition temperature between anhydrite and gypsum to

be in the range of 56 58 C. This is incongruent with the

results of Partridge and White (1929); however, all the
works (Blount & Dickson, 1973; Hardie, 1967; Partridge
& White, 1929) seemed to indicate that in the range
of operation of majority of industrial heat exchangers,
gypsum is the dominant phase. Furthermore, Hasson and
Zahavi (1970) proposed a correlation for CaSO4 nucleation times and reported that nucleation of anhydrite
is an extremely slow process in comparison to that of
gypsum. This also justi=es considering gypsum as the
dominant phase. Correlations for solubility products for
di/erent forms of calcium sulfate, which may be adjusted

T. H. Chong, R. Sheikholeslami / Chemical Engineering Science 56 (2001) 53915400

4. Results and discussions

Table 1
Summary of batch tests conditions

5393

Run

T ( C)

CaCO3 (M)

CaSO4 (M)

BT1
BT2
BT3
BT4
BT5
BT6
BT7
BT8
BT9
BT10
BT11
BT12
BM1
BM2

70
60
60
70
70
60
70
60
80
80
80
80
60
70

0.030
0.030
0.020
0.020
0.022
0.022
0.028
0.028
0.030
0.020
0.022
0.028
0.000
0.000

0.000
0.000
0.010
0.010
0.008
0.008
0.002
0.002
0.000
0.010
0.008
0.002
0.030
0.030

for the appropriate temperature, are available in the

literature (EPRI, 1982; Marshall & Slusher, 1968;
Nordstrom et al., 1990).
3. Experimental techniques
Batch tests were carried out with model solutions with
total calcium content of 0:03 M and sulfate concentrations
ranging from 0 to 0:01 M at temperatures of 60, 70 and

80 C. Table 1 lists the chemical composition of model

solutions used in experimentation.
The supersaturated solutions of calcium sulfate
(CaSO4 ) and calcium carbonate (CaCO3 ) were prepared
by adding equimolar amounts of Na2 SO4 and CaCl2 ,
and CaCl2 and NaHCO3 , respectively. The solutions
were prepared with analytical grade chemicals and with
micro-=ltered (with 0:22 m Millipore =lter) distilled
water. Solution pH was measured before mixing, then
the mixture was carefully transferred to a series of 75 ml
test tubes; which had been scrubbed, rinsed with concentrated hydrochloric acid and washed thoroughly with
distilled water; to avoid air bubbles formation as the air
bubbles will a/ect the equilibrium of CO2 hence the
concentration of CO2
3 in the solution. One tube sample
was removed right after mixing the individual solutions,
=ltered with 0:22 m =lter and was analysed for water
quality. Water quality was determined by measurement
of pH, total alkalinity, hardness (by complexometry),
and sulfate (by chromatography) using the standard
methods of water analysis. Remainders of the tubes were
placed in the temperature baths. Water quality was monitored for each sample taken during the run. To ensure
constant volume reaction for the kinetic data analysis,
for each sample two solution-=lled tubes were removed
from the bath and used for the analysis and monitoring
during the run. The water quality tests were carried out
until equilibrium had been achieved.

4.1. General observations

For all the runs when the solutions of CaCl2 ; NaHCO3
and Na2 SO4 were mixed, the mixture immediately turned
into a cloudy solution. This indicated the formation of a
white colour CaCO3 precipitate and also a very insignificant nucleation or induction period that is reasonable
for such a supersaturated solution. Besides, the amount
of precipitate collected during =ltering of pure CaCO3
was less compared to the mixture of CaCO3 + CaSO4 .
In addition, as the concentration of CaSO4 increased, the
amount of precipitate collected increased as well. This
was due to the fact that pure CaCO3 is a very adherent
scale, where most of the precipitate stuck to the wall of
test tube as was observed. The presence of CaSO4 weakened the CaCO3 scale, making the precipitate less tenacious and freely moving in the solution. Therefore, the
scale formed from the mixture could be more easily removed than that of the pure CaCO3 scale. This is consistent with previous =ndings of Bramson et al. (1996) in
their study of composite fouling of CaCO3 and CaSO4 on
a heat transfer surface in turbulent Jow of a falling =lm.
4.2. Scale morphology
The CaCO3 scale was a powdery-like precipitate while
CaSO4 had a needle shape. The pure CaCO3 crystal had
a hexagonal structure, which indicated that the CaCO3
was in the form of calcite and proves that it was the
favourable form of calcium carbonate precipitation phase.
When CaSO4 was added to the CaCO3 , the needle shape
crystals grow on the hexagonal crystal. The pure CaCO3
crystals were more tenacious and compact than the mixed
solutions. Also, more crystals were grown in the pure
CaCO3 as compared to the mixture.
4.3. E4ect of sulfate ion and temperature on calcium
decline
Total calcium concentration of the solutions was monitored in order to investigate the co-precipitation e/ects
and to determine the solubility constants for salt mixtures. The e/ect of solution composition at given temperatures are shown in Fig. 1. The change in total cal
cium concentration for all solutions at 60 C are shown in
Fig. 1(a) and shows that the crystallisation process exhibited no induction period; all the curves have a steep decrease in Ca2+ at the initial stage of the experiment before
reaching equilibrium. The e/ect of sulfate on precipitation is compared with that of pure CaCO3 solution (BT2)
in which Ca2+ concentration decreased from the initial
value of 1200 ppm (0:03 M) to the equilibrium concentration of 552 ppm (0:0138 M) in about 500 h indicating

5394

T. H. Chong, R. Sheikholeslami / Chemical Engineering Science 56 (2001) 53915400

sulfate concentration increases, the solubility concentration of calcium increases as well and the e/ect of sulfate
gradually levels-o/ as its concentration increases.
Figs. 1(b) and (c), respectively show the e/ect of co

precipitation at 70 C and 80 C and Table 2 summarizes

increases in =nal calcium concentration and the percent
age drop in precipitate for all the runs. Again, at 70 C and

80 C, presence of sulfate increased the equilibrium concentration of calcium and reduced the amount of precipitation but the e/ect levelled-o/ as it approached 0.008

0:010 M. The only di/erence was that at 80 C, the amount

of precipitate for the solution with 0:008 M of SO2
4 was
slightly (less than 1%) higher than that for the solution
with 0:010 M of SO2
4 . This is very likely due to experimental errors and is negligible.
The e/ect of temperature at given concentrations are
shown in Fig. 2. As expected for inverse solubility salts,
the equilibrium concentration for calcium decreased as
the solution temperature was increased irrespective of
concentration of SO2
4 and the solution composition.
4.4. Decline in concentrations of anions
and SO2
Concentrations of anions (CO2
3
4 ) are required to determine the solubility products for CaCO3 and
CaSO4 salts in the co-precipitation process. The CO2
3
were calculated from the distribution of carbonic species
in solution based on the total alkalinity and pH of the
solution as follows
[CO2
3 ]=
2
Fig. 1. E/ect of composition (
at 0:000 M SO2
4 , at 0:002 M SO4 ,
2
2
4 at 0:008 M SO2
,
at
0:010
M
SO
and

at
0:002
M
SO
4
4
4 )
at given temperatures.

approximately 54% (648 ppm) had precipitated. When

0:002 M of SO2
4 was introduced to the CaCO3 solution
(BT8), the equilibrium concentration for Ca2+ shifted
to 632 ppm indicating a decline of 7% in the amount
of precipitate (568 ppm) from 54% to 47%. Further increase in sulfate concentration to 0.008 (BT6) and 0:01 M
(BT3) reduced the total amount of calcium precipitated
to, respectively, 468 and 460 ppm. This indicates as the

[T:A:] + [H+ ] [OH ]

;
2(1 + [H+ ]=2K2 )

[HCO2
3 ]=
[CO2 ] =

(1)

[T:A:] + [H+ ] [OH ]

;
(1 + 2K2 =[H+ ])

(2)

[T:A:] + [H+ ] [OH ]

;
K1 =[H+ ](1 + 2K2 =[H+ ])

(3)

2
CT = [HCO
3 ] + [H2 CO3 ] + [CO3 ]:

(4)

Based on the electroneutrality condition through the proton balance equation, the Total Alkalinity (T.A.) of water
with a total carbon species CT is
2

+
[T:A:] = [HCO
3 ] + 2[CO3 ] + [OH ] [H ]:

(5)

Table 2

on Ca++ concentration in solution and precipitation

E/ect of SO
4

SO2
4

60 C

(M)

Final Ca++
(ppm)

Precipitate
% decrease

Final Ca++
(ppm)

Precipitate
% decrease

Final Ca++
(ppm)

Precipitate
% decrease

0.000
0.002
0.008
0.010

552
632
732
740

0
7
15
16

520
592
700
716

0
6
15
16

512
552
700
696

0
3
16
15

70 C

80 C

T. H. Chong, R. Sheikholeslami / Chemical Engineering Science 56 (2001) 53915400

5395

Fig. 3. Carbonate ion concentrations in the solutions (
at

2
2
and
at
0:000 M SO2
4 , at 0:002 M SO4 , 4 at 0:008 M SO4
2
0:010 M SO4 ).

Fig. 2. E/ect of temperature (

at given compositions.

at 60 C,
at 70 C, and 4 at 80 C)

By combining Eqs. (1) (5) the concentration of each

carbon species can be obtained. The declines in concentrations of anions are represented in Figs. 3 and 4, re
2
spectively for CO2
3 and SO4 at 60, 70 and 80 C. The
2
initial quantity of CO3 in the solution was unknown because the HCO
3 in the solution prepared from sodium
and CO2
bicarbonate powder will dissociate to CO2
3

according to the chemistry of carbonic acid which is

pH dependent. We cannot obtain this value by using
relationships for pure sodium carbonate as the pH of
concentration upon
solution changes and a/ects CO2
3
mixing sodium bicarbonate and calcium chloride solutions. So though the exact initial value could not be determined, the instantaneous values were calculated and
plots exhibare shown in Fig. 3. In general, the CO2
3
ited similar trends to those of Ca2+ . By increasing the
ions or in other words decreasing the CO2
in
SO2
4
3
had
the solution, the equilibrium concentration of CO2
3
had suppressed
been increased. The presence of SO2
4
ions
the crystallisation of CaCO3 , leaving more CO2
3
in the solution. This indicates that the e/ect of sulfate
on CaCO3 solubility is not due to pH e/ects as both
Ca2+ and CO2
3 solubilities are increased in presence of
sulfate.

5396

T. H. Chong, R. Sheikholeslami / Chemical Engineering Science 56 (2001) 53915400

4.5. Solubility product

Fig. 4. Sulphate ion concentrations in the solutions (4 at

at 0:008 M SO2
and
at 0:010 M SO2
0:002 M SO2
4 ,
4
4 ).

The change in SO2

4 content in the solution with time
(Fig. 4) was less pronounced than that of CO2
3 . The
at
lowest
sulfate
concenaverage total change of SO2
4
tration of 0:002 M was about 30 ppm only. At highest
sulfate concentration of 0:01 M, the amount precipitated
had
was more signi=cant and about 250 ppm of SO2
4
crystallized with Ca2+ .

Table 3 summarizes the results for solubility products

of pure salts and mixed solutions. Also pure salt data determined in this study are compared with the published
(Bott, 1995; Marshall & Slusher, 1968) values. The measured values for pure CaCO3 are greater than those of
literature (Bott, 1995) and for pure CaSO4 are lower than
those in the literature (Marshall & Slusher, 1968). The
di/erence can be due to the method of solution preparation and analysis; in this study, all CaCO3 and CaSO4
solutions were obtained by mixing CaCl2 , NaHCO3 and
Na2 SO4 solutions while the previous researchers determined the Ksp from pure crystals. In the following
discussion, the measured values are used to compare the
solubility constants in mixtures with those in pure salts
to ensure consistency; however, this would not have any
e/ect on the trends obtained even if the literature values
were to be used.
The results show that the solubility product of CaCO3
in the co-precipitation process is greatly a/ected by the
presence of CaSO4 . For example, by introducing 0:002 M

SO2
4 into the solution at 70 C the Ksp value for CaCO3
8
increased to 1:943 10 , by about 500% from the Ksp
(3:00109 ) for pure salt. The Ksp of CaCO3 in mixed so
lutions with 0.008 and 0:01 M CaSO4 at 70 C increased,
respectively, by 1205% and 1329% from that of pure
CaCO3 . The Ksp for CaSO4 was also calculated for all the

runs with sulfate. The Ksp for pure CaSO4 at 70 C was

1:760105 while in a mixed solution with minor amount
of sulfate (0:002 M) the Ksp had dropped by about 75% to
4:308 106 . While for the solutions with higher concentrations of sulfate (0.008 and 0:01 M), the Ksp in mixed
solutions were very close (between 1% and 10%) to of
those in pure calcium sulfate solution. Fig. 5 shows a
graphical representation of the trend between the Ksp s at

60 C for each salt in the mixed solution in comparison

to those of pure salts. The same trends were observed at
other temperatures. It is very clear that the solubility constant of the dominant calcium carbonate is greatly a/ected
by presence of calcium sulfate and the e/ect levels-o/ as
the concentration of the non-dominant anion increases.

Table 3
Solubility product for CaCO3 and CaSO4 (CaCO3 Dominant)
Ksp for CaCO3

Ksp for CaSO4

Solution

60 C

70 C

80 C

CaCO3 (Bott)
0:030 M CaCO3 (measured)
0:028 M CaCO3 + 0:002 M CaSO4
0:022 M CaCO3 + 0:008 M CaSO4
0:020 M CaCO3 + 0:010 M CaSO4
0:030 M CaSO4 (measured)
CaSO4 (Marshall and Slusher)

1.821E-09
4.011E-09
1.962E-08
4.000E-08
4.408E-08

1.386E-09
3.000E-09
1.943E-08
3.915E-08
4.288E-08

1.056E-09
1.910E-09
1.715E-08
3.415E-08
3.557E-08

60 C

70 C

80 C

5.051E-06
1.907E-05
2.076E-05
1.930E-05
3.594E-05

4.308E-06
1.795E-05
1.921E-05
1.760E-05
3.244E-05

3.615E-06
1.692E-05
1.870E-05
2.889E-05

T. H. Chong, R. Sheikholeslami / Chemical Engineering Science 56 (2001) 53915400

As seen in previous discussion, the equilibrium concentration of both Ca2+ and CO2
3 ions has increased in presence of sulfate. The e/ect on the non-dominant ion is
much less though cannot be neglected at some ratios of
non-dominant to dominant ions. This means the Ksp values for the pure salts are not suitable to be used when predicting the equilibrium established in a co-precipitating
system.
The e/ect of presence of foreign coprecipitating ionic
species upon the thermodynamic solubility constant of
pure salt could be explained from the thermodynamic
aspect. The formation of pure CaCO3 from Ca2+ and
CO2
3 proceeds according to the reaction below
Ca2+ + CO2
3  CaCO3 (s):

5397

Fig. 5. Comparison of Ksp for both salts in pure and mixed solutions.

(6)

At equilibrium, the Gibbs free energy of reaction (Rr G)

is zero. Therefore based on Eq. (7), at equilibrium the
thermodynamic solubility constant will be related to the
standard molar Gibbs free energy of reaction (Rr G
)
according to Eq. (8)

a 2+ a 2 
Ca
CO3
;
(7)
Rr G = Rr G
+ RT ln
aCaCO3
RT ln(Ksp ) = Rr G
:

(8)

a is the activity of ions or salt, R is the universal gas

constant and T is temperature in Kelvin. By de=nition,
Rr G
is the di/erence between the total standard Gibbs
free energy of formation of products Rf G
(products)
and the reactants Rf G
(reactants). For the formation of
CaCO3 , the following equation can be written:
Rr G
= Rf G
(CaCO3 ) {Rf G
(Ca2+ )
+Rf G
(CO2
3 )}:

(9)

In the coprecipitation process, the product di/ers from

that of single salt precipitation. This is supported by the
scale morphology of salt forms from mixture where the
needle-shaped CaSO4 grows in the hexagonal-shaped
CaCO3 . For the sake of reference, the product in
co-precipitation is denoted by an asterisk (CaCO3 ).
Since the standard Gibbs free energy of formation of
that mixed salt Rf G
(CaCO3 ) is di/erent from that of
the pure salt Rf G
(CaCO3 ), hence the thermodynamic
equilibrium constant of the coprecipitation is di/erent
from that of single salt precipitation.
The solubility product of salts for all solutions decreased with increasing temperature, as both salts are of
inverse solubility characteristic. For the pure CaCO3 , the
Ksp determined from the experimental data was 4:011

109 and decreased by 25% and 52% for 70 C and 80 C,

respectively. As mentioned previously, the di/erence in
the measured and literature values for pure salts are expected to be due to the e/ect of sample preparations.
The solubility constants for both salts were =tted to
vant Ho/ equation (Atkins, 1995) to obtain correlations

Fig. 6. Solubility constants for both salts.

with respect to temperature and also to obtain the heat of

precipitation (RHR ) based on the following relationship:
d ln(Ksp )
RHR
=
:
(10)
d(1=T )
R
The plot of ln(Ksp ) vs. 1=T should yield a straight line
with a slope equal to RHR =R, where R is the universal
gas constant. Fig. 6 shows the plots for both CaCO3 and
CaSO4 . The correlations showing the e/ect of temperature are given in Table 4.
As seen in Fig. 6(a), the slope of the curves for
pure measured and literature (Bott, 1995) values of
CaCO3 were very similar though the Ksp values were
slightly higher. This indicates comparable heats of
precipitation. In addition, Table 4 shows that the heats

5398

T. H. Chong, R. Sheikholeslami / Chemical Engineering Science 56 (2001) 53915400

Table 4
Equations of Ksp for CaCO3 and CaSO4 (CaCO3 Dominant)
Solution composition
CaSO4

CaCO3

0:000 M
0:002 M
0:008 M
0:010 M

0:030 M
0:028 M
0:022 M
0:020 M

Ksp (CaCO3 )

Ksp (CaSO4 )

ln(Ksp ) = 4:353 103 =T + 32:37

ln(Ksp ) = 7:858 102 =T + 20:09
ln(Ksp ) = 1:195 103 =T + 20:35
ln(Ksp ) = 1:252 103 =T + 20:67

ln(Ksp ) = 1:966 103 =T + 18:09

ln(Ksp ) = 7:036 102 =T + 12:98
ln(Ksp ) = 6:175 102 =T + 12:64

of precipitation for both CaCO3 in solutions with 0.008

and 0:01 M CaSO4 were almost the same. Likewise,
the heats of precipitations for CaSO4 in these solutions
were almost the same. These were the solutions that
exhibited almost the same Ksp values at given temperatures. So, one hypothesis might be that the presence
of a co-precipitating salt with a common cation somewhat a/ects the heat of precipitation and therefore the
extent of precipitation and this as discussed before can
be explained from the standard Gibbs free energy of the
substance produced.
4.6. Rate of precipitation for CaCO3
Fig. 2 shows that there was a sharp decline in the concentration of Ca2+ initially right after the solutions were
mixed; for example in Run BT8, Ca2+ in the solution
dropped to 0:0212 M and 29% of initial Ca2+ precipitated
in less than 2 min. The decline in Ca2+ became more gradual as the time progressed. Runs (BT1, BT2, BT7, BT8,
BT9 and BT12) with high levels (0.03 and 0:028 M) of
CaCO3 showed a rapid decrease in the =rst 50 h before
approaching equilibrium. To study CaCO3 precipitation
process under the inJuence of CaSO4 and temperature,
the rate constant associated with each run was calculated. The initial attempt was to use the integral approach
and to =t the data to 2nd order reaction that had been
suggested (Nancollas & Reddy, 1971) for pure calcium
carbonate. Therefore, according to a second-order reaction (Eq. 12) between Ca2+ and CO2
3 (Eq. 11), the plot

of log(d[Ca2+ ]=dt) vs. log({[Ca2+ ][CO2
3 ] Ksp })
should yield a straight line with the slope of 1 and the
intercept of log(kr ).
k

r
Ca2+ + CO2
3 CaCO3 (s);

d[Ca2+ ]

= kr {[Ca2+ ][CO2
3 ] Ksp }:
dt

(11)
(12)


in Eq. (12) is the concentration product of Ca2+ and
Ksp
2
CO3 at equilibrium. The experimental data shown in
Fig. 7 (a) indicated that there was a region, known as
initial surge growth, where the crystallisation rate could
not be predicted by Eq. (12). This initial surge was also
noted by Nancollas and Reddy (1971) who thus suggested applying Eq. (12) to the rate of crystallization but

Fig. 7. Assessment of rate of precipitation for calcium carbonate (

at 60 C,
at 70 C, and 4 at 80 C).

excluding the initial surge period and through this obtained linear relationship with slope of unity. Therefore,
the same approach of excluding the initial surge period
was used (as shown in Fig. 7(b)); however, the slopes
of the plots were greatly di/erent from unity. This would
mean that the crystallisation rate of calcium carbonate in
presence of calcium sulfate could not simply be modelled
as a second order reaction. This suggests that using the
rate equations suggested for a single salt crystallization
to crystallization of mixed salts might as well be questionable. Controlled experiments and possibly continuous monitoring of calcium concentration (e.g. by calcium
electrode) is necessary to provide more precise measurements for kinetic analysis during the very early stages
and hence determining the rate and order of reaction.
5. Concluding remarks
The e/ect of water quality is of great importance on
induction times and precipitation of calcium carbonate.
Also the presence of other cations or anions that may form

T. H. Chong, R. Sheikholeslami / Chemical Engineering Science 56 (2001) 53915400

particulate matter plays a signi=cant role in promoting

precipitation of a salt solution due to the aGnity that
the salt has to precipitate on other particulate matter in
preference to, say, the heat transfer surface. The species
will tend to do this long before homogeneous nucleation
becomes a viable option. Nevertheless work has mainly
been in the absence of other precipitating species and
correlations have been established where nucleation has
been achieved homogeneously.
In this study, the e/ect of co-precipitation of calcium
carbonate and calcium sulfate in a solution having CaCO3

as the dominant salt was investigated at 60, 70 and 80 C.

In presence of CaSO4 , the CaCO3 scale which is usually very adherent and tenacious loses its strength and
becomes less adherent and more freely moving. Also,
in solution increases the equilibrium
presence of SO2
4
concentration of both Ca2+ and CO2
3 and therefore the
solubility constant for CaCO3 . The thermodynamic solubility constant of pure salt precipitation is di/erent from
that of the co-precipitation due to the fact that the product of co-precipitation di/ers from that of single salt
precipitation; based on thermodynamic principles, it is
hypothesized that this is related to the change in standard molar Gibbs free energy of reaction Rr G
. This
is evident from the structure of the product of mixed
calcium carbonate and sulfate solution that showed the
growth of needle-shaped CaSO4 in the hexagonal-shaped
CaCO3 .
The solubility constant for CaCO3 increases with increase in sulfate ion but there seems to be a limit to the
e/ect of CaSO4 on CaCO3 precipitation. This is evident
from the experimental runs with 0.008 and 0:01 M CaSO4
where the e/ect of SO2
had levelled-o/. Presence of
4
CaCO3 had a di/erent e/ect on CaSO4 solubility. In solutions with minute amounts of sulfate (0:002 M), the
CaSO4 solubility product in the mixture was much less
than that of pure salt. However, further increases in the
sulfate concentration to 0:01 M, has increased the CaSO4
solubility constant in the mixture to that of pure salt.
Therefore, these suggest that the thermodynamic data for
pure salts are not extendable to co-precipitation; also it
seems that the e/ect depends on the dominance as well.
Experimental measurements are necessary until theoretical studies will address the co-precipitation issue. Also
additional tests are necessary to verify the existence of
critical composition range where Ksp s are una/ected by
composition.
The solubility product of pure CaCO3 determined experimentally was slightly higher than those reported by
Bott (1995) while that of pure CaSO4 was slightly lower
than those reported by Marshall and Slusher (1968). This
di/erence could be due to the e/ect of sample preparation; in this study, all CaCO3 and CaSO4 solutions
were obtained by mixing CaCl2 ; NaHCO3 and Na2 SO4
solutions while the previous researchers determined the
Ksp from pure crystals of calcium carbonate and calcium

5399

sulfate. This suggests that there are two di/erent constants for dissociation and association of salt.
Solubility products for both salts were correlated with
temperature using vant Ho/ relationship (Atkins, 1995).
Heat of reaction was similar for solutions with 0.008 and
0:01 M of CaSO4 that exhibited similar solubility constants. This again may suggest and reinforce the hypothesis that presence of non-dominant ion a/ects the heat of
precipitation.
Kinetic data for calcium carbonate did not correspond
to a second-order reaction as suggested in the literature
(Nancollas & Reddy, 1971). But from the concentration
pro=le of the species, it was shown that there was an
initial surge followed by an exponential decrease before
reaching equilibrium. It is possible that the extent of supersaturation had caused this. It is highly recommended
to study the change in [Ca2+ ] and [CO2
3 ] at the initial
stage of crystallisation to examine what is the extent of
the surging process. Also the applicability of 2nd order
reaction rate should be examined with either less supersaturated solutions or with Ca2+ monitoring with electrochemical method that would permit more accurate measurements during initial periods.
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