DESALINATION

ELSEVIER Desalination 137 (2001) 275-284

www.elsevier.com/locate/desal

Thermodynamic description of saline waters - Prediction of

scaling limits in desalination processes

B. Hamrouni a*, M. Dhahbi b

aD~partement de Chimie, Facult$ des Sciences de Tunis, Campus Universitaire, 1060 Tunis, Tunisia
Tel. +216 (1) 872600; Fax +216 (1) 885008; e-mail: bechir.hamrouni@fst.rnu.tn
Laboratoire de Physico-Chimie des Interfaces, INRST, BP 95, 2050 Hammam-lif, Tunisia
Tel. +216 (1) 430044; Fax +216 (1) 430934; e-mail: mahmouddhahbi@inrst.rnrt.tn

Received 2 August 2000; accepted 5 September 2000

Abstract

A thermodynamic modeling of saline waters is achieved taking into account acid-base, ion associates formation
and precipitation equilibrium. A microcomputer program, written in the graphical language LabView accomplished
the necessities of iteration for the solution of simultaneous equations, calculations. Extended Debye-Htickel and
Pitzer models were used for the activity coefficient calculations. The program allows determining the repartition of
free ions, ion pairs, and weak acid species. Calcium carbonate stability of water was predicted thanks to calco-
carbonic equilibrium curves calculation. Concentration factors for calcium carbonates, calcium sulfates and silica
were also calculated. The calculations were carried out for different kinds of saline waters at different temperatures.
For representative calculations, standard seawater and brackish feed water for a reverse osmosis desalting plant in
Gab~s region (in South Tunisia) were selected.

Keywords: Activity coefficient; Mineral scaling; Calco-carbonic equilibrium; Concentration factor; LabView

1. Introduction like South Tunisia (North Africa) an adequate

supply o f fresh water is o f primary importance.
To sustain the commercial, agricultural and
Production of fresh water from seawater and
social development in arid and semi-arid regions
brackish water has proved to be an alternative
for these regions. Desalination processes, by
*Corresponding author.
distillation or by membrane techniques such as

Presented at the 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 Ecole Nationale d'lngenieurs de Tunis, September 11-13, 2000, Jerba

0011-9164/01/$- See front matter © 2001 Elsevier Science B.V. All rights reserved
PII: S 0 0 1 1 - 9 1 6 4 ( 0 1 ) 0 0 2 2 9 - 6
276 B. HamrounL M. Dhahbi /Desalination 137 (2001)275-284
electrodialysis and reverse osmosis, are based on
the concentration principle. So, in saline water
desalination, scale prevention is an integral part
of the design, operation, and the cost of
desalination plants. The presence of scale leads
invariably to operating difficulties and/or loss of
efficiency. In MSF evaporators, sealing of heat
exchanger tubes reduces the heat transfer
coefficients and flow rates, while in RO system,
scaling of membranes results in decreasing plant
efficiency by restricting water flow and
decreasing product quality. The accumulation of
scales in the different parts of a desalting plant
reduces its overall efficiency and increases its
capital cost. The cost increase may be equivalent
to about 10% of the whole capital cost of the
plant [1].
Exact knowledge of the solubilities of the
most common minerals such as calcium
carbonate, calcium sulfates and silica, in brackish
waters and seawater, is vital since the solubility
determines whether the brine is saturated or not.
It is necessary to calculate the solubility product
constant for the sparingly soluble salts in the
concentrate stream to determine if they present a
potential sealing problem. The main factors
affecting scale formation is salt concentration [2],
operating temperature [3-5], fluid velocity [5-7],
pH of water environment [3,4,6] and time [6].
The aim of this study is the prediction of the
most common scale forming salts such as calcium
carbonate and calcium sulfate, by developing a
microcomputer program. This practical tool may
be useful for desalination users to calculate
concentration factor (CF) and caleo-carbonic
equilibrium curves. This needs a complete
thermodynamic description of saline waters. The
number of possible free ions, associated ions
(complexes and ion-pairs) and the necessity of
iteration for the solution of simultaneous
equations and the calculation of activity
coefficients make the use of computer methods a
real necessity. The microcomputer program,
written in LabView graphical language uses,
according to the ionic strength of the treated
water, either the extended Debye-Hiickel model
or the Pitzer ion specific interaction model to
calculate ion activity coefficients.
The program was applied to different saline
waters at different temperatures. For repre-
sentative calculations standard seawater and a
brackish feed water and permeate of a reverse
osmosis desalting plant, in South Tunisia, were
selected.
2. Equilibrium modeling of saline waters
In most high salinity waters, for example
seawater, the principal ionic species are the
cations Na ÷, K ÷ and Mg 2+ and the anions C1- and
SO42-. In contrast to these principal species, the
weak acid-base systems, carbonic and silicic
acids, governing pH, contribute minimally to the
ionic strength of such solutions. Considering the
distribution of species in such highly saline
aqueous solutions, generally it is accepted that
OFF and an appreciable fraction of the weak acid
species SO42-, CO32-, HCO3- form ion pairs (and,
in the case of SO42-, triple ions) with the cations
Mg2+, Ca2+, Na +, For K ÷ ion pairs and triple ions
are formed with SO42-. Ion pairing between these
cations and CI- has been considered insignificant.
2.1. Equilibrium equations
The behavior of weak acid-base systems is
intimately involved in the control of the pH and
precipitation phenomena. The example of carbo-
nic acid system is presented here.
CO2aq + H 2 0 <::>H2CO 3 (1)
H2CO; <::>H ÷ + HCO; (2)
HCO; <=~H + + CO 2" (3)
 B. Hamrouni, M. Dhahbi /Desalination 137 (2001) 275-284 277

(.+)[.co;] m o)-rco, (4)

Mass balance equations are illustrated by
total concentration of calcium and sulfate:
KI= [COz] =Kl° YHC%

H CO~] Ynco;
(5)
[Ca2+]r= [Ca2+](i+ Kc~so°[SO2]+Kc~co3[CO~
]
K2
: _, I H c ° ; i : K° (13)
YcoJ
K. = ( . + ) [ o H l = K ° (I'I20) (6) + [o.] 1
YOH" K ca~co~- K c~on÷ J
Associations between anions and cations are
illustrate by the following equilibrium equations [SO] ]r = [SO]" I1 + KM,so0[Mg2+
] + Kc~so0[Ca2+
]
of ion pairing of the sulfate species by divalent
cations Mi l+ (Mg2+, Ca1+) and monovalent (14)
cations Mi+ (Na+, K+): +
K N~so; K Na2SOo K Kso; K K,soo J
Mi 2+ MiSO
Mi + + SO 2- ¢=>~MiSO] (7)
2Mi + [(Mi)2 SO ° + ion triple 2.2. Activity coefficients models

For which the equilibrium constants are: The Poisson Boltzman equation and the
Debye-Htickel theory (DH) are the basis of a
number of successful semi-empirical equations
[Mi2+][SO-V]- K ° YMiSO'° (8) for a variety of thermodynamic properties [8].
KMiSO° = [MiSO° ] - MiSO°Y~+-Yso~" The more popular of these are discussed in the
references [9,10]. Perhaps the most widely
applicable of these equations are those developed
[Mi+][SO~]_ K0 ?'~so~ by Pitzer and coworkers since 1973 [8]. Pitzer
K~so; = [MiSO~] - vaso;
Yv,i+ -Ysoi" (9) [11,12] discusses the origin of these equations
and their application in some detail. The Debye-
Htickel model, which can be used to estimate the
[Mi2+][SO~-] = KO 7~so~ (10) activity coefficient of a highly diluted electrolyte
KMi2SO [Mi2SO0]
= 2soi aqueous solution, was the foundation on which
y~+ • Yso~.
Pitzer's theory was built. The general formulation
Mineral scaling equilibrium is given for of the Pitzer model is principally made up of two
calcium sulfate: parts in terms of excess Gibbs energy. The first
corresponds to the Debye-Hilckel model, which
CaSO4, xH20(solid) <::>Ca 2+ + 8 0 2- + xH20 (11) are a function of ionic strength and the dieleclric
constant of the solvent. The second part takes
K ° =(Ca 2+)(SO42")(H20) ~ = K r .rso, (U O) (12) into account of the binary and ternary inter-
actions neglected in the initial Debye--Htickel
where x=0 for anhydrite, x=0.5 for hemihydrate model which Pitzer introduced and formulated in
and x=2 for dihydrate or gypsum. order to describe the behavior of solutions at
278 B. Hamrouni, M. Dhahbi /Desalination 137 (2001) 275-284

high concentrations. The total excess Gibbs
energy presents in the form:
G~ - f ( I ) + Z j Z . ~ . u m , mj
nwRT , j
+ ~ ~ ~ /~tmimjmk
j k
where fl/) is a function of ionic strength,
expressing the effect of the long-range electro-
static forces; 2 # - second virial coefficient,
depending on ionic strength, expressing the effect
of the short-range forces between species i and j;
mijk - - third virial coefficient, independent of
ionic strength, expressing the triple ion inter-
actions.
The activity coefficient equations are obtained
by appropriate derivations. These equations are
rearranged in terms of which are determined by
The subscripts M, c and c' refer to cations and
the subscripts X, a and d to anions. The summa-
tion index, c, denotes the sum over all cations in
the system while the double summation index,
c<c', denotes the sum over all distinguishable
(15) pairs of dissimilar cations. Analogous definitions
apply to the summation indices for anions X, a
and d and for neutral molecules N and n. B a n d f
represent measurable combinations of the second
virial coefficients 2. C and 9' represent measur-
able combinations of the third virial coefficients
/~. B and C are derived from single electrolyte
data. ~band 9"are derived from tow-salt systems.
To include interaction with neutral species N,
terms are added to the expressions of in?~'vtand
lnyx. The activity coefficients of neutral species
N, where in solution there are nc cations and na
anions, are given by:
lie na

adjustment with experimental data. This leads to In ?u = Z m~(2,;/m~)+ Z m,, (22N,,) (18)
the following equations giving ionic activity c=i a=l

coefficients for cations Mand anions X:

lnT'M = Z 2 F + ~".m~(2Blvta + ZCM~) 3. Results and discussion

a

The program developed in this work was

(16) applied to different saline waters at different
temperatures to perform various useful calcula-
+ ZZm~mo,9,a~.M + Z M Z Z m c m , C¢~ tions such as:
a< a ~ c a
• Dissolved species activity coefficients and
water osmotic coefficient, at different temp-
In?' x = Z 2 F + ~mc(2B~x + Z C ~ ) eratures,
c
• Free and ion paired species distribution,
(17) • Calco-carbonic equilibrium curves CO2r =
fl[Ca~+]),
• Concentration factors of sparingly soluble
+ Z Z m ¢ m ~ , ~ ¢ , x +[ZxlZZmomoC~o
c< cI c a salts,
• Variation of the concentration factors with
where temperature.

z=Zm, lz, l=2Zmcz, =Zmalzol For representative calculations, synthetic

i c a standard seawater, brackish feed water and
permeates from a groundwater desalination plant
 B. Hamrouni, M. Dhahbi /Desalination 137 (2001) 275-284 279

Table 1
Composition of synthetic seawater and analyses of feed water, permeate and concentrate fxomGab6s desalination plant

Parameters Synthetic seawater Gab~ d~dination plant

Feed water Permeate Concentrate
TDS, mg/L -- 3224 182 8938
pH 8 7.4 7.5 7.4
Temperature, °C 25 23 23 23
Turbidity, NTU -- 0.3 0.17 0.16
TH, OF -- 129.7 4.9 361.4
Ca2+,mg/L 426 393.6 11.62 1103
Mg2+,mg/L 1345 76.5 4.86 209.4
Na+, mg/L 11202 446 17 1266
K+, mg/L 40 42 2 113.5
CO32-, mg/L 0 0 0 0
HCO3-, mg/L 167 111 41.7 229.6
CI-, mg/L 20168 795.2 40.1 2189.9
S042-, mg/L 2794 1019 5.76 3070.5

in Gab6s region, in South Tunisia (Gab6s 3.1. Calculation procedure

desalination plant) were selected. Composition
o f standard seawater and analyses o f feed water,
permeate and concentrate from Gab6s desa-
lination plant are reported in Table 1. This desa-
lination plant, with a production of 22,500m3/d,
operates on the basis of reverse osmosis process
and is supplied with hot brackish water from
deep wells o f 700 to 900m depth.
To test the developed program, calculation
results were compared with available experi-
mental values for standard synthetic seawater.
To illustrate the calculations performed, the
program was applied to the feed water and the
permeate o f Gab6s desalination plant.
In general, the program checks the introduced
water composition according to the electro-
neutrality o f the salt aqueous solutions. The
calculation procedure and the representative
results, relative to the developed program, are
presented in the following sections.
The necessary input data for the program
were:
• Total molar concentrations o f principal
species.
• Thermodynamic equilibrium constants for
acid-base species, associated ions (ion pairs,
triple ions and complexes) and solubilities
product for minerals able to precipitate.
• The pH and the total inorganic carbon (or
other equivalent measurable parameter).
The calculation procedure is an iterative one
involving the following successive steps:
(a)Total species concentrations were used to
estimate the initial ionic strength and starting
values for species activity coefficients.
(b) Thermodynamic constants were adjusted for
activity coefficient effects to give apparent
equilibrium constants.
280 B. Hamrouni, M. Dhahbi /Desalination 137 (2001)275-284
(c)Fee and associated species concentrations
were determinate from mass balance con-
siderations.
(d) Ionic strength was recalculated based on the
species concentrations determinate above.
(e) Activity coefficients were determinate using
separately the extended Debye-Hiickel model
or the ion specific interaction model of Pitzer.
(f) The procedure from step (b) to step (e) was
repeated until successive values for the ionic
strength agree to within three significant
figures.
(g) For each mineral, initial concentration factor
(CF) was estimated.
(h)The water was concentrated CF times and
procedure (f) was repeated until successive
values for concentration factor agree to within
two significant figures.
(i) Output: activity coefficients, water osmotic
coefficients, species distribution, calco-
carbonic equilibrium curves, concentration
factors.
The assumptions used, because of the lack of
data, in activity coefficient determinations were:
• Neutral ion paired species were assumed to
have activity coefficient equal to unity.
• Single charged ion paired species were
assumed to have activity coefficients equal to
that for Na +.
The started concentration factors for calcium
carbonate mean that the treated water is saturated
or nearly saturated with the correspondent
mineral. So these concentration factors are to be
taken equal to unity.
The graphical language LabView from
National Instruments was used to carry out all
the calculations. LabView uses terminology, icons
and ideas familiar to scientists and engineers and
relies on graphical symbols rather than textual
language to describe programming actions.
LabView has extensive functions libraries and
subroutines for most programming tasks [13-
16].
3.2. Example of preliminary calculations
Activity coefficients were calculated using
the extended Debye-Hiickel model (EDH)
according to the following Eq. (19) and to the
Pitzer model according to the Eqs. (16-18):
logT',- Az2' "f-i + b,I (19)
1 + a °BqtI
Single ion activity coefficients calculated, for
the major electrolyte component in synthetic
seawater (Table 1), from various seawater models,
are reported in Table 2. Garrels et al. and
Truesdell et al. [18] adopted the Bjerrum ion
association hypothesis. Their results and those
obtained in this paper using the extended Debye-
Htickel equations wander from experimental
values. These models may be useful for more
diluted saline solutions than seawater [8,27].
Whitfield used the Br6nsted-Guggenheim hypo-
thesis of specific ionic interaction, without taking
into account interactions between ions of like
charge [ 18]. Pitzer made a significant advance of
this model. His model is accurate to ionic strength
above 4 m, when the third virial coefficients are
included [26,27]. Our results, using Pitzer model,
are in good agreement with the experimental
values.
Calculations of the distribution of the major
constituents of seawater and feed brackish water
(Gab~s desalination plant) were carried out giving
free ion and ion paired species percentage. In
Table 3, percentages of free ions are given for
these two kinds of water. The calculated dis-
tribution shows the importance of ion pairs
formation in seawater as well as in brackish
water. In these two cases CO32-, HCO3-, SO42-
and Mg 2+ are the most affected by ion pairing
formation.
3.3. Calco-carbonic equilibrium curves
The caleo-carbonic equilibrium study was
based on the graphical representation, of Legrand
 B. Hamrouni, M. Dhahbi /Desalination 137 (2001) 275-284 281

Table 2
Single ion activity coefficientscalculatedfrom various seawatermodels

Reference Component
Na+ K+ Mg2+ Ca2+ CI- SO42-

Garrels et al. [17] 0.752 0.634 0.313 0.255 0.640 0.065

Truesdell et al. [ 18] 0.705 0.618 0.287 0.247 0.618 0.176
This paper (EDH model) 0.706 0.619 0.288 0.248 0.619 0.177
Whitfield [ 19] 0.643 0.600 0.222 0.199 0.690 0.120
This paper (Pitzer model) 0.640 0.599 0.206 0.190 0.691 0.121
Experimental [20--25] 0.67 [20] 0.61 [21] 0.26 [22] 0.21 [23] 0.68 [24] 0.11 [25]

Table 3
Percentage of frcc ionic species in seawater and in feed brackish water

Species SO4 2- CI- HCO3- CO2 2- Na+ K+ Mg2+ Ca2+

Seawater 49.9 100 72 9.6 92.2 94.4 83.3 92.8

Brackish water 77 100 92.2 20.1 99.3 97.6 70 83.7

and Poirier [28,29], of the total dioxide carbon 28.5 mg per one liter of permeate is necessary to
concentration [CO2T] vs. calcium concentration reach calco-carbonic equilibrium.
[Ca2÷]. This representation was chosen,
among others, for its convenience and for ~n-
allowing the direct prediction of chemicals I,li.
quantifies to be added to bring the given water to
equilibrium. The calculate curve for the permeate, I 12-
from Gabrs desalination plant, collected in a
basin o f 2 , 5 0 0 m 3 capacity prior to distribution, is
D.4..
presented in Fig. 1. The figurative point M of the
permeate, which composition is given in Table 1, O,D
o~t " o3 J o'a ' o'? " o~; '
shows that this desalted water was not in equi- O " ~ 10~ added ~ ~Ca~J,,w~Ul..
librium and was aggressive. This is in con-
Fig. 1. Calco-carbonic equilibrium curve for permeate
cordance with analytical tests and with observed
from Gabrs desalinationplant.
action o f this water on the storage basin material.
Using the calco-carbonic curves and as
indicated on the Fig. 1, it is easy to predict the
3.4. Concentration factors calculation
quantities o f chemicals to be added t o bring this
water to equilibrium corresponding to point M'. For any desalting process, concentration factor
This may be reached by addition o f lime, soda or CF may be defined as the ratio of salinities of
calcium carbonate. If lime is used, a quantity of concentrate to feed water. Calculated CF, to
282 B. HamrounL M. Dhahbi /Desalination 137 (2001) 275-284

avoid precipitation of gypsum (CaSO4, 21-120),

H z a ~ h y d n ~ (H) . .
hemihydrate (CaSO4, 0.5H20) and anhydrite
(CaSO4), from standard seawater and brackish
water are plotted against temperature respectively ~o- ~ -....._ ^~=.~,....,
in Figs. 2 and 3. Some available experimental
values of CF in seawater [30-32] were plotted
together with calculated values. A good
agreement was observed and the small difference
I: ~.o- y" GA)
ii
could be due to slight differences in composition.
°'~o ~[o ~.o 7to Mxo lzko tim
For ambient temperatures, seawater is con- Tnmpecat~ ~

siderably undersaturated with respect to dihydrate

Fig. 2. Calcium sulfate concentration factors for standard
and may be concentrated at least three. From
seawater.
Fig. 2, the transition temperatures of conversion
of dihydrate to anhydrite and dihydrate to
hemihydrate are respectively about 35°C and 4.0-

100°C.
3.0-
At 25°C, the composition of feed brackish
water, of Gab~s desalination plant, leads to a
concentration factor value of about 2 (Fig. 3). To
operate without gypsum precipitation, the con-
version rate must not exceed 50%. As this
condition is not economically acceptable, amount
of calcium must be removed to prevent precipi-
i 7.O-
1..%
1.0.
0~-

°'~o~o z~.o ~o
T ~
Anla~ltit~

7io
' C
i~o 1~o l~o
tation. Therefore, antiscalant treatment is used in
Gab~s desalination plant, which can operate at a Fig. 3. Calcium sulfate concentration factors for brackish
conversion rate of 75% corresponding to a water from Gab~s desalination plant.
concentration factor value of 4.

users. This program may perform, based on the

4. Conclusion input water composition, rapid evaluation that
A microcomputer program was developed for could allow immediate adjustment in operating
the calculation of chemical equilibrium, in saline conditions.
waters, and for the estimation of the concen-
tration factors to avoid precipitation of minerals
such as calcium sulfates, calcium carbonates and 5. Symbols
silica. It may be updated, by the user, as a more )~ - - Activity coefficient of species i
adequate model for calculating activity (0 - - Activity of species i
coefficients becomes available or by including [O, [Or - - Free and total concentration of
other minerals of interest. The kinetic study of species i, respectively
the precipitation and the stay time of brine A, B --Debye--Hiickel parameters for the
phenomena may complete our thermodynamic activity coefficients
approach. However, the results of this work 0
ai - - Distance of closed approach between
constitute a practical tool for desalting plant hydrated ions
 B. Hamrouni, M. Dhahbi /Desalination 137 (2001) 275-284 283

b~ - - Adjustable parameter for ion i added [6] J.G. Knudsen, Fouling in heat exchangers, In:
to the Debye-Hfickel equation Hemisphere Handbook of Heat Exchangers Design,
G~ - - Excess free energy G.F. Hewitt, ed., 1990.
I - - Ionic strength o f solution [7] S.G. Yiantsios, N. Andritsos and A.J. Karabelas,
K,°, K~ - - T h e r m o d y n a m i c and apparent equi- Presented at Fouling Mitigation of Industrial Heat
librium constant for the ionization Exchangers Engineering Foundation Conference,
number i o f carbonic acid, respec- AIChE and ASME, CA, USA, June 1995.
tively [8] J.1LLoche and M.D. Donohue, AIchE J., 43 (1997)
K ° , Ks - - Thermodynamic and apparent 180.
equilibrium constant for calcium [9] J.F. Zemaitis, Jr., D.M. Clark, M. Rafal and N.C.
sulfate solubility, respectively Scrivner, Handbook of Aqueous Electrolyte
K ° , Kw - - Thermodynamic and apparent Thermodynamics,DIPPR, A1ChE,New York, 1986.
equilibrium constant for water [10] M. Rafal, J.W. Berthold, N.C. Scrivner and S.L.
ionization, respectively Grise, Models for Electrolyte Solutions, Models for
Thermodynamic and Phase Equilibria Calculations,
In, l o g - - N e p e r i a n and decimal logarithm,
S.I. Sandier, ed., Dekker, New York, 1994.
respectively
[11] K.S Pitzer, Ace. Chem. Res., 10 (1977) 372.
m~ - - Molality o f species i
[12] K.S. Pitzer, On Interaedon Approach: Theory and
n~, nw - - N u m b e r o f mole o f species i and
Dam Correlation, Activity Coefficients in Electrolyte
number o f kilograms o f water,
Solutions, 2nd ed., Ch. 3, K.S. Pitzer, ed., CRC Press,
respectively
Boca Raton, 1991.
pH - - - log(IT)
[13] IL Gostowski,J. Chem. Education, 73 (1996) 1103.
R - - Gas constant 8.314 J.K-l.moF 1
[14] S.M. Drew, J. Chem. Education, 73 (1996) 1107.
T - - Absolute temperature in Kelvin
[15] M.A. Muyskens, S.V. Glass, T.W. Wietsma and
TDS - - Total dissolved salts T.M. Gray, J. Chem. Education, 73 (1996) 1112.
TH - - Total hardness [16] P. Orgen and T.P. Jones, J. Chem. Education, 73
z~ - - Charge o f ion i (1996) 1115.
[17] R.M. Garrels and M.E. Thompson, Am. J. Sci., 260
(1962) 57.
[18] A.H. Truesdell and B.F. Jones, J. Res. US Geol.
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