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DESALINATION

/ 1

II
ELSEVIER

Desalination 152 (2002) 167-174

w ww.elsevier.com/locate/desal

Calco-carbonic equilibrium calculation

B. HamrotmP*, M. Dhahbi b
D~partement de Chimie, Facultd des Sciences de Tunis, Campus Universitaire, 1060 Tunis, Tunisia
Tel. +216 (71) 872600; Fax +216 (71) 885008; email: bechirhamrouni@fst.rnu.tn
bLaboratoire de physico-chimie des interfaces, INRST, B.P 95, 2050 Hammam-Lif, Tunisia
Tel. +216 (71) 430044; Fax +216 (71) 430934; email: mahmouddhahbi@inrst.rnrt.tn
Received 1 April 2002; accepted 15 April 2002

Abstract
The Langelier and the Stiff-Davis saturation indices have found wide acceptance as indicators of the degree of
water saturation with respect to calcium carbonate. But the risk of aggressiveness or scaling may be accurately
evaluated from the analytical data by application either of the graphic methods or the complex methods of calculation
made possible by the use of data processing. The present work was devoted to the study of this problem using a
computerized model of Legrand and Poirier, based on the plot of the CO2 concentration vs. Ca2 concentration.
Taking into account the formation, in natural waters, of ion pairs as well as the various equilibrium constant variation
with temperature made improvements to this model. Consequently the ionic activity coefficients were calculated
using suitable models. Calculation was developed by means of the graphical LabViewTM programming language.
The calco-carbonic curves obtained constitute a useful tool to visualize if the studied water was in equilibrium or not
and provide quantitative indications of how much reagent, such as lime or soda, must be added to bring water to
equilibrium. Calculations carded out with the program were illustrated by some results and compared with those of
Legrand and Poirier and others studies.

Keywords." Calco-carbonic equilibrium; Saturation indices; Calcium carbonate; Activity coefficient; LabView
1. Introduction
The most important weak acid-base system is
the carbonate one as it is intimately involved in
the control of the pH, exchange of CO 2 between
*Corresponding author.

air and water and precipitation phenomena in

waters. Exact knowledge of different salts solubility
in natural waters, brackish waters, seawater and
geothermal waters, is vital since the solubility
determines whether the water is saturated or not
[1-5].

Presented at the EuroMed 2002 conference on Desalination Strategies in South Mediterranean Countries:
Cooperation between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean.
Sponsored by the European Desalination Society and Alexandria University Desalination Studies and Technology
Center, Sharm El Sheikh, Egypt, May 4-6, 2002.
0011-9164/02/$- See front matter 2002 Elsevier Science B.V. All rights reserved
PII: S 0 0 1 1 - 9 1 6 4 ( 0 2 ) 0 1 0 5 9 - 7

168

B. Hamrouni, M. Dhahbi / Desafination 152 (2002) 167-174

The scales commonly encountered in the

desalination of natural waters are usually composed of calcium, magnesium and barium salts
of sulfate, hydroxide, and carbonate. Calcium
carbonate may precipitate from water in one or
more of three forms: calcite, aragonite and vaterite.
Which of these allotropes precipitates depends
on the pressure, the temperature, the presence of
foreign ions and the rate at which precipitation
takes place [6-9]. The calcite polymorph of calcium
carbonate is the most common scale-forming
mineral. Results from a number of studies involving
spontaneous precipitation reveal that, at moderate
temperatures, vaterite is the solid phase forming
first during the precipitation process. The predominance of one crystalline phase over the other
depends on conditions such as pH, temperature,
and the nature of the antiscalants present [10-13].
At higher temperature, though calcite is the most
thermodynamically stable phase, aragonite has
been reported to be the first phase to precipitate
from solution [14].
Water is said to be saturated with calcium carbonate when it is neither dissolve, nor precipitate
calcium carbonate scale. This equilibrium condition
is based upon undisturbed water, at constant temperature, which is allowed to remain undisturbed
for an infinite period of time. Water is said to be
undersaturated if it can still dissolve calcium
carbonate. Supersaturated water will precipitate
calcium carbonate from water if allowed to rest.
The aim of this study is the calculation of the
calco-carbonic equilibrium to predict the behavior
of the water towards calcium carbonate, by developing a microcomputer program. This practical
tool may be useful for different users to establish
the calco-carbonic equilibrium curves which provide
a more accurate way to determine ira water is in
calco-carbonic equilibrium or not. If it is aggressive or scaling it is easy to deduce quantitatively
the appropriate chemical treatment. The microcomputer program written in LabView graphical
language uses the extended Debye-Htickel model
to calculate ion activity coefficients. The effects
of ion pairing and temperature on the true ionic

strength of the treated water and on equilibrium

constants calculation, were taken into account.
The results of the program were compared to those
of Legrand-Poirier and applied to different waters
at different temperatures. For representative
calculations geothermal water from the south of
Tunisia, mineral water and permeate water from
a reverse osmosis desalting plant, were selected.

2. Thermodynamic aspects of caclco-carbonic

equilibrium
2.1. Carbonic system

Basically the carbonic system is derived from

the dissolution of carbon dioxide and carbonate
minerals into the water. Thus, the carbonate system
is a weak acid-base system which exists in aqueous
solutions as dissolved carbon dioxide CO.zaq,
carbonic acid H2CO3, bicarbonate HCO3-, carbonate
ions CO32- and complexes of these ions such as
CaliCO3 +, CaCO 3.
Dissolved carbon dioxide are hydrated in few
minutes [15,16] according to the reaction:
CaCO3aq + H20 :~ CO2, I-I20

(1)

The term H2CO3 refers to the composite form,

which is the sum of the activities of molecularly
dissolved carbon dioxide CO2aq, and the hydrated
form CO 2, H20:
(H2CO3) = (CO2aq) q- (CO 2, H20)

(2)

This composite form is convenient because of

the analytical difficulties of separating out CO2a
from CO 2, H20 which constitute about 3% o~
H2CO3 [17].
The behavior of carbonic system is intimately
involved in the control of the pH and precipitation
phenomena by the following equilibrium relationships:
H2CO 3 ~

H + H C O 3-

(3)

H C O 3- :~ H+ CO32-

(4)

C a 2+ + CO32- ~:::::~C a C O 3

(5)

13. Hamrouni, M. Dhahbi / Desalination 152 (2002) 167-174

[H+][HC07]

=K o

[H2CO3]

-]

~/u:co,

_K,

(6)

- K2

(7)

TW'YHCO;

- Ko

[HCO3]

[Ca>][CO]-]_

r.co
3'H+~'CO~-

_&

(8)

(H+)[ OH- ] = Kw(H20) = Kw

(9)

~/ca-,+~/co?

'YOHThe behaviour of specific water towards

CaCO 3 (marble) defines its scaling or aggressive

nature. If we consider, for a given temperature,

the following equilibrium:
CaCO 3 + H2CO 3 :~ 2HCOf + Ca 2+

(10)

When the amount ofH2CO 3increases for some

reason the equilibrium will move to dissolve the
calcium carbonate (the water is said aggressive).
When the quantity ofH2CO3 is less than the quantity
needed for the equilibrium then CaCO 3 precipitates (the water is said scaling).
2.2. Calco-carbonic equilibrium representation

The risk of aggressiveness or scaling of calcium

carbonate may be evaluated by different ways:
From the analytical data by application of the
graphic methods and indices calculations,
From the analytical data by the complex methods
of calculation made possible by the use of microcomputers,
From laboratory tests.
Many saturation indices are used as indicators
of the degree of water saturation with respect to
calcium carbonate [5]: Langelier saturation index,
Ryznar stability index, Puckorius scaling index,
Larson-Skold index and Oddo-Tomson index.
The most widely used indices are those of Langelier

169

and Stiff-Davis. For example, Langelier saturation

index (LSI) is the result of a mathematical formula
using arbitrary numbers that are assigned to five
factors - - pH, total alkalinity, calcium hardness,
total dissolved solids and temperature. LSI is applied
to low salinity waters and the Stiff-Davis saturation
index is mostly used for high salinity waters.
On the other hand, diagrams giving calcocarbonic curves are proposed by many authors,
among them Langelier [18], HaUopeau [19,205,
Roubais [21 ] and Legrand and Poirier [22,23.]. In
the present work the more recent representation
of Legrand-Poirier was chosen, among others, for
its convenience and for allowing the direct prediction of chemical quantities to be added to bring
the given water to equilibrium.
2.3. Legrand-Poirier presentation

For establishing their diagram ofcalco-carbonic

equilibrium, Legrand and Poirier [22,23] distinguished between what they call:
Fundamental elements found in all natural
waters and result of atmospheric CO 2 interaction with calcium: H30 +, HCO3- , OH-, H2CO3,
Ca 2+, CO32-.
Characteristic elements whose presence
characterizes any natural water: Mg > , K +,Na +,
NOr, SO42-, Cl-.
The following relation gives the electric neutrality of the medium:
2[Ca2+1+ [H30+] + 2[Mg >] + [K+]
+ [Na +] = [NO,-] + 2[so4=-] + [Cl-]
+ [HCO3-] + 2[CO32-] + [OH-]

(11)

where concentrations are expressed in mole or

mmol/l of solution. The authors used the parameters
N, P and ~, as follows:
p = 2[Mg >1 + [K+] + [Na+1
N = [NO,-] + 2[8042-] + [El-]
N-P
2

(12)

170

B. Hamrouni, M. Dhahbi/ Desalination 152 (2002) 167-174

Neutrality equation is:

2~CaZ+ ] - Z,)
= [ H C O 3 ] + 2[CO ~-] + [OH- ] - [H 30 + ]

3. R e s u l t s a n d d i s c u s s i o n

(13)

with
[CO2 ]r = [H2CO3 ] + [ H C O 3 ] + [CO23- ]

(14)

and
[CO2 ]r = 2([ Ca2+] - k) + [H3O+ ]
-

[OH- ]-

[CO~- ] +

[H 2 C 0 3 ]

(15)

The free carbonic species concentrations are:

[CO2]r[H+] 2
[H2CO3]- [H+] 2 +K~[H+]+K, K2

(16)

[CO2]r[H+]KI
[HCO3] = [H+]2 +K,[H+]+K, K2

(17)

[CO2]TKIK2
[CO]-] = [H+] 2 +K~[H+]+K~K2

(18)

From these equations and the solubility product

of calcium carbonate [Eq. (8)], the authors built
their caico-carbonic equilibrium diagram by plotting
the total dioxide carbon concentration [CO2]r vs.
calcium concentration [Ca2+]. Each point of the
curve obtained represents particular water in
equilibrium. Thus the space is subdivided into two
regions: aggressive waters on the left and scaling
waters on the right.
In their representation Legrand and Poirier
made the following hypothesis:
All the ions are considered to be free without
ion pairing
Activity coefficients are supposed to be independent of temperature, and the same for
different ions.
These hypothesis lead to erroneous ionic strength
and apparent equilibrium constants.

3.1. Improvement to Legrand-Poirier representation

The calco-carbonic equilibrium study was baseA
on the graphical representation of Legrand and
Poirier [22,23], of the total dioxide carbon concentration [COJr vs. calcium concentration [Ca2*].
To improve this representation calco-carbonic
calculation was modified by introducing the effect
of ion pairing on the ionic strength and on the
apparent equilibrium constants, and by using a
more accurate model for activity coefficients
depending on ion nature and temperature.
Our previous calculated distribution of the
major constituents of seawater and brackish water
showed the importance of ion pairs formation in
seawater as well as in brackish water [3,4]. In
these two cases CaCO32-, HCO3-, SO42-and Mg~+
are the most affected by ion pairing formation. The
most important associated ionic species encountered
are: CaSO2, MgSO4, NaSO4-, KSO4-, Na2SO4,
K~SO4, MgHCO3+, CaliCO3+, MgCO3, CaCO3,
NaCO3-, MgOH% CaOH +, NaOH .
In this way the true ionic strength takes into
account the free and associated (ion pairs) charged
species:
1

I = - ~ Z i [ionic free species]L

2 i
+ 1 ,~ Z2[charged ion pairs ]

(19)

At finite dilution deviations from ideality are

observed and the activity and concentrations are
no longer equal and they are linked by the activity
coefficients. Among the available models for the
activity coefficients calculation [3,4], the extended
Debye-Htickel model was used according to the
following equation:
logy i = -

A.z, 47
l+aO.B~

+b~ .I

(20)

When the concentration [COJr is not available,

B. Hamrouni, M. Dhahbi / Desalination 152 (2002) 167-174

(21)

f) for each value of total carbon dioxide concentrations, steps (c) to (e) were repeated.
g) output: calco-carbonic equilibrium curves
COsT =f([Ca2+]) and calco-carbonic treatment to
bring water to equilibrium.

(22)

3.3. Calco-carbonic curves establishing

the total carbonic species concentration calculation

may be based on the knowledge of the total alkalinity
(TA), Eq. (14) and the following relations:
[HCO3]r = [HCO3]L + ~-'~M,HC03
i

[CO2-]r = [CO~-]L + )-'~M, CO3

i

where M are cations susceptible to give ion pairs

with H C O [ and CO3 z-.
The total alkalinity may be linked to species
concentration by le following expression:
T A = [ O H - ] + [ M g O H +] + [CaOH +]

+ [HCO 3 ] + [CaliCOS ] + [MgHCO~ ]

+ 2[CaCO ] + 2[MgCO~ ] + 2 [ N a C 0 3 ]

171

Different kinds of water were used to perform

representative calculations. Composition of these
waters, namely, synthetic water, desalinated water
and geothermal water, are reported in Table 1. The
synthetic water given as an example by Legrand
and Poirier [22] was used for comparison. Desalinated and geothermal waters were from South
Tunisia.

(23)

+ [ N a O H ] + [ N a H C O ] ] - [H + ]

Table 1
Composition and analyses of the different waters used for
illustrations
Parameters

3.2. Calculation procedure

The program developed in this work checks

the introduced water composition according to the
electroneutrality of the salt aqueous solutions. The
different steps of the iterative procedure necessary
to perform the calculations were:
a) input of total molar concentrations of principal species, thermodynamic equilibrium constants
for acid-base species, associated ions (ion pairs,
triple ions and complexes) and solubility product
for calcium carbonate, temperature.
b) ionic strength and lambda were calculated
based on total species concentrations choice of
starting value for total carbon dioxide concentrations.
c) after pH initialization, activity coefficients
and apparent equilibrium constants were calculated.
d) free and associated species concentrations
and the ionic strength were determined.
e) after pH increment, steps (c) and (d) were
repeated until calcium carbonate ionic product
equalled apparent equilibrium constant for its
solubility.

pH
Temperature,C
Na+, mmol/L
K , mmol/L
Ca2,mmol/L
Mg2+,mmol/L
CI-, mmol/L
SO42-, mmol/L
CO32-, mmol/L
HCO3-, mmol/L

Type of water
Synthetic Desalinated Geothermal
-7.5
?
18
23
62
0.12
0.74
14.6
0.1
0.05
1.07
-0.29
6.3
0.05
0.20
2.91
0.3
1.13
19.0
0.8
0.06
7.29
-0
0
-0.68
2.33

The simplified version of the developed program

permits reaching more easily and more quickly
the results of Legrand and Poirier. Calculations
obtained by the modified version were compared
with those given for synthetic water by the same
authors. Table 2 summarizes the results indicating
important deviation that confirms the importance
of taking into account the ion pair formation. In
this case at least 10% of total calcium are associated with bicarbonate, carbonate and sulfate ions.
An example of establishing equilibrium calcocarbonic curves is given in Fig. 1 in the case of

172

B. Hamrouni, M. Dhahbi / Desalination 152 (2002) 167-174

Table 2
Comparison between our results and those of Legrand and Poirier [22]
Parameters
[CO2]r
pHs
Ca2+[22]
Ca2+this work
Deviation, %

1.0
8.1
1.30
1.21
6.9

2.0
7.7
1.77
1.68
5.2

3.0
7.4
2.21
2.11
4.7

6.0
7.0
3.37
3.19
5.7

2.0-
1.816-

1.41,2~1.0408-

0.0-

0.0

j
/

rep..... taivepointJ
~rbo!c

12.0
6.6
5.12
4.68
9.4

15.0
6.5
5.83
5.25
11.0

20.0
6.4
6.83
6.03
13.3

30.0
6.2
8.45
7.24
16.8

Table 3
Two series of marble test for the desalinatedwater

regionwherewaters
(CaCO3arc
corroslvedissolution)

-- 02-0"4"0'6-

9.0
6.8
4.32
4.02
7.6

Parameter

regionwherewatershave
tendencytoscale
(CaCO3-Vtecipitation)

pH

TA, F

TH, F

Without CaCO3 5.9

5.5

0.46
0.45

0.21
0.18

With CaCO3

3.95
3.75

3.94
3.40

8.2
8.2

_ equilibri
l ........

01

0.2

0.3

0.4

0.5

0.6

0.7

[Clt2+] I ~ L

0.8

09

1.0

Fig. 1. Calco-carbonicequilibriumcurvesestablishing,case
of a permeate water at 25C from South Tunisia.
desalinated water by reverse osmosis from South
Tunisia. This figure shows the position of the water
representative point (dark point) in relation to the
equilibrium curve dividing the space in two regions
corresponding to aggressive waters on the left and
scaling waters on the right.
The experimental results of the marble tests,
obtained after 24 h for the desalinated water, are
given in Table 3. Increasing values observed for
pH, total alkalinity (TA) and total hardness (TH)
mean that the water has tendency to dissolve CaCO 3.
This conclusion confirms the position of the representative point on the left of the calco-carbonic
curve as predicted in Fig. 1.
In Fig. 2, two equilibrium curves were drawn
for the geothermal water taken at its extraction
temperature 62C and when cooled to 18C. It
appears that this water is nearly in calco-carbonic
equilibrium at 62C but becomes aggressive at
18C. This indicates the important effect of

20.0-

ioo_
~ 14.012.010.0~ 8.06.04.02.00.'

s.o

6'.o

71o

8'.0

9'.o

1;.o

11.o

i~2+ I IUT

Fig. 2. Calco-carbonicequilibrium curves for a geothermal

water from South Tunisia, at 62 and 18C.
temperature in the study of the behaviour o f given
water towards calcium carbonate.
3.4. Example o f calco-carbonic treatment
To bring water to calco-carbonic equilibrium
many reagents may be added such as lime, caustic
soda, calcium carbonate and sodium carbonate.
For example, calculations were deduced from calcocarbonic curve of desalinated water in the case of
post-treatment by lime, calcium carbonate and

B. Hamrouni, M. Dhahbi / Desalination 152 (2002) 167-174

1.81.62.0-

m / ' 1 ~

I.2-

o.6-

0.4-

0.20.0

o'.~ o b
[Ca2~h,mml
~. [Ca2+Jn,,al

c.3

,
,
0.4 o.s
[CaS+l I

o'.6

'
0.7

"0.8

Oig

Fig. 3. Determinationof lime quantity necessary to bring

the desalinatedwater to caico-carbonicequilibrium.

2.0- .
1.81.6-

1.4-

I 12-

173

After the improvements and refinement made, the

computerized representation of Legrand and Poirier
chosen was convenient and quantitative. Improvement was made by taking into account the ion pair
formation, temperature effect and by performing
adequate activity coefficient calculations. The
comparison of our results with the original method
confirms the importance of the modifications
made. The application of the program to different
kinds of water at different temperatures shows
that it constitutes a more accurate and rapid way
to know the behaviour of a given water towards
calcium carbonate. Moreover, it permits, using
the calco-carbonic curves, choosing the treatment
and calculating the quantity of reagent necessary
to bring water to calco-carbonic equilibrium. Taking
into account kinetic considerations may complete
the thermodynamic approach followed in this work,
which can be improved.

o.o-

Symbols

4,B
O0

.I

ol0

o/:!,.o:2

f-=-~

r-

o,

L. [Ca2~]initinl =l
L~ [Ca?L]final__~___~

06

00

,0

let'*n ,moUL

Fig. 4. Determination of calcium carbonate quantity

necessary to bring the desalinatedwater to calco-carbonic
equilibrium.
sodium hydroxide. For illustration, Figs. 3 and 4
show the examples of treatment by lime and
calcium carbonate respectively. It is easy to deduce
that the quantities needed to bring the studied
water to calco-carbonic equilibrium are per liter:
4.5 mg of lime or 8 mg of sodium hydroxide or
13 mg of calcium carbonate.
4. Conclusion

The different saturation indices and other

graphical methods constitute simple indicators for
the behaviour of water toward calcium carbonate.

- - D e b y e - H t i c k e l parameters for the

activity coefficients
a i
- - Distance of closed approach between
hydrated ions
bi
- - Adjustable parameter for ion i added
to the Debye--Hackel equation
1
Ionic strength of the solution
Free and total concentration ofi species,
[i], [i]r
respectively
- - Activity of species i
(0
ro,&
Thermodynamic and apparent equilibrium constant for calcium carbonate
respectively
K 0,Kv - - T h e r m o d y n a m i c and apparent equilibrium constant for water ionization
respectively
K , K
Thermodynamic and apparent equilibrium constant for the ionization
number i of carbonic acid respectively.
pH.~
- - log(H+)s, pH of solution saturated by
CaCO 3
TA
- - Total alkalinity

174
TH
Zi

v,

B. Hamrouni, M. Dhahbi / Desalination 152 (2002) 167-174

- - Total hardness
-Charge o f ion i
Activity coefficient o f i species

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