ISBN # 0-9745019-9-9

A New Index for Scaling Assessment

Authors: HANNACHI Ahmed, Naimi Imen, ZINOUBI Raoudha, ELFIL Hamza

Presenter: HANNACHI Ahmed, Assistant professor, National Engineering School of Gabes, Tunisia.

Abstract

Water treatment and desalination practices have shown that predictions of the CaCO3 scaling risk lack
accuracy. In fact most of the saturation indices and models used so far for scaling assessment have some
limitations. This limited success in predicting the scaling can be fairly attributed to the fact that most of
the used indices are based on the thermodynamics data of calcite. However, experimental investigations
have shown that the calcite which is considered to be the most stable form of the six calcium carbonate
allotropic varieties is not involved in the CaCO3 nucleation. Actually the CaCO3 hydrated forms
(Amorphous Calcium Carbonate: ACC; Monohydrate Calcium Carbonate: MCC and Hexahydrate
Calcium Carbonate: HCC) and not the anhydrous forms (calcite, aragonite and vaterite) were revealed to
be crucial precursors for calcium carbonate spontaneous nucleation. The solubility products of the MCC
and the ACC were proven to constitute lower limits for spontaneous and instantaneous nucleation
respectively in the temperature interval ranging between 20 and 60C.

Based on the thermodynamics data of the monohydrate calcium carbonate form, a novel scaling index
was established and referred to as the Monohydrated form Langelier Saturation Index (MLSI). The
ability of the MLSI to correctly predict the scaling phenomenon for brackish as well as desalination
reject waters was verified and compared to that of the well-known Langelier Saturation Index (LSI) and
the Stiff and Davis Stability Index (SDSI) for several experimental results in the scaling field. Unlike the
LSI and SDSI, the MLSI was able to predict the non scaling water behavior. Thus, scaling assessment
based on the MLSI values will eventually lead to rationalize the use of chemicals and help avoiding
membrane calcium carbonate scaling in desalination units.

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I. INTRODUCTION

CaCO3 scaling is a complex phenomenon for which many aspects have to be unfolded. Water treatment
and desalination practices have shown that all available scaling risk evaluation methods have some
limitations. The scaling phenomenon has long been at the heart of much of the research effort on water
and related problems. Since the early work of Langelier [1], many scaling prediction models and indices,
such as the Ryznar Index and the Poirier and Legrands model, have been developed [2-7].

In most investigations, water scaling properties were established when opposing actual water
composition and that of water at a thermodynamic equilibrium state. Consequently, many scaling
saturation indices have been put forward. However, since these scaling models have a limited success in
evaluating the scaling risk, many empirical scaling indices have also been developed [8-10].

Whether empirical or fundamental, all the available models have some limitations in predicting the
scaling risk [7, 11-12]. These limitations are inherent to the complexity of the system involving several
equilibrium relations at the solid/liquid and liquid/gas interfaces, for which very few reliable
thermodynamic equilibrium data were available. The major weakness is related to the fact that only
calcite, the thermodynamically most stable calcium carbonate form, was considered in saturation indices
expressions. But experimental investigations have shown that largely surpassing the saturation with
respect to calcite (aragonite and vaterite) does not systematically induce any spontaneous precipitation
phenomena [13-14]. In fact, the calcium carbonate has a total of six allotropic forms three of which are
anhydrous forms. The anhydrous phases are crystalline polymorphs (calcite, aragonite and vaterite), the
other three calcium carbonate phases are hydrated forms (Amorphous Calcium Carbonate: ACC,
Monohydrate Calcium Carbonate (MCC): CaCO3.H2O and Hexahydrate Calcium Carbonate (HCC):
CaCO3.6H2O). According to recent experimental investigations, the ACC was shown to be a precursor
for instantaneous CaCO3 nucleation at high supersaturation while the MCC was shown to be a precursor
for CaCO3 nucleation at low supersaturation [14, 15]. This fact has been accounted for in the recently
introduced saturation index referred to as the Monohydrated form Langelier Saturation Index (MLSI)
[16].

In the desalination field, two scaling indices are usually used to assess the scaling tendency of brine
water. While the Langelier Saturation Index (LSI) is often applied for brine solutions of a TDS not
exceeding 10 g/L, the Stiff and Davis Saturation Index (SDSI) [2] is used to assess the scaling tendency
of highly saline solutions such as those encountered in see water desalination. In this work, the ability of
the novel saturation index to correctly predict the calcium carbonate scaling phenomena will be
compared to that of the LSI and SDSI for brackish water and for highly saline water such as that of the
brine in reverse osmosis desalination units.

II. SCALING INDEX FORMULATION

LSI and SDSI are both equilibrium models derived from the theoretical concept of saturation. They were
established by comparing water composition to that at a thermodynamic equilibrium state. The solution
pH is compared to that of a calcite calcium carbonate saturated solution. These two saturation indices
have the same defining relation:

SI = pH - pHS (1)

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With respect to scaling tendency, Langelier and Stif & Davis concluded that if:

- pH - pHS > 0 water is scaling and CaCO3 is likely to precipitate

- pH - pHS = 0 water is at equilibrium at the considered temperature.
- pH - pHS < 0 water is aggressive and has tendency to dissolve CaCO3.

For the Langelier Saturation Index, the saturation pH is calculated from the water Ca2+ concentration,
alkalinity (Alc) and the apparent equilibrium constants as follows:

pHS = -log [Ca 2+ ]-log[Alc] + C (2)

In this equation, the parameter C is obtained empirically [17] and derived from equilibrium apparent
constant as a function of the Total Dissolved Salt (TDS) and the absolute temperature T.

While the LSI is used solely for low salinity and/or ionic strength solutions, The SDSI was derived for
high saline water and high ionic strength solutions. In this index, the parameter C derived from the
solubility product and the carbonic acid dissociation constant is replaced by an empirical constant K that
depends on the ionic strength [18].

These saturation indices account only for the CaCO3 calcite form. Despite their large use in the
desalination field, the LSI as well as the SDSI do not access the scaling tendency correctly often leading
to an over consumption of chemicals to prevent the scaling phenomena.

A recent saturation index that accounts for the precursor role, and particularly that of the monohydrated
form, in CaCO3 scaling has been recently introduced [16]. This scaling index, referred to as the MLSI, is
derived from the same relation (1) and the saturation pH is obtained from the equilibrium constants of
the solubility product and the 2nd carbonic acid dissociation given by:

K S = (CO 32- ) (Ca 2+ ) (3)

(CO 32- )(H 3 O + )

K2 = (4)
(HCO 3- )
Giving the facts, that the MCC solubility product constitutes, between 25 and 60C, a lower limit that
must be exceeded to obtain a spontaneous germination [13, 15], the saturation pH is calculated using the
CaCO3.H2O solubility product instead of that relative to calcite. For a pH ranging between 6 and 9, it is
written as:

pH S/MCC = pK 2 pK S/MCC log Ca 2+ log HCO log[Ca 2 + ] log[Alc] (5)

3

Where pHS/MCC and pKS/MCC are the monohydrate calcium carbonate saturation pH and solubility product,
respectively.

As the previous indices, the MLSI is then defined as follows:

MLSI = pH - pHS/MCC (6)

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To assess the scaling character of water, three critical values of the MLSI have to be considered. Besides
zero, two MLSI threshold values have been introduced according to the following defining equations:

- MLSIinst is given by the same equation (6) when substituting pHS/MCC by the amorphous calcium
carbonate (ACC) saturation pH, pHS/ACC. Surpassing this value is an indication of a highly scaling
behavior as the ACC was shown to be a precursor for CaCO3 nucleation at high supersaturation [13,
19].
- MLSIagr is also given by the same equation when replacing the pHS/MCC by the calcite saturation pH,
pHS/calcite, which is exactly the saturation pH defined by Langelier.

The scaling/equilibrium/aggressive state of a Ca-carbonic water as function of MLSI values can be

classified as follows:

MLSIinst < MLSI;
0 < MLSI < MLSIinst;
MLSIagr <MLSI < 0
MLSI < MLSIagr,
Water is highly scaling and the phenomenon is instantaneous (at 30 C
MLSIinst = 0.74).
Water is scaling; the phenomenon depends on the wall nature and will be
slow for MLSI values close to 0.
There is no spontaneous precipitation; water is at a Ca-carbonic
equilibrium (at 30 C MLSIagr = -1.32).
Water is under saturated with respect to calcite and can be considered as
aggressive.

The activity coefficients are calculated using adequate models according to the solution salinity. For
water solution of an ionic strength not exceeding 0.2 (TDS < 10 g.L-1), the extended Debye-
Hckel model [20] can be used. For much higher salinities encountered in reverse osmosis desalination
units, where the ionic strength is close to 1, the Pitzer model can be used to obtain the activity
coefficients for the existing cations and anions. In fact this model is known to be available up to an ionic
strength of 6 [21].

III. EXPERIMENTAL INVESTIGATION

An experimental investigation was conducted. It was intended to unfold the scaling behavior of several
water qualities similar to those encountered in reverse osmosis desalination units. The calco-carbonic
solutions were synthetic solutions prepared by dissolving pure CaCO3 in distilled water or by mixing
calcium chloride and sodium carbonate solutions according to the desired concentration levels. To
obtain the proper ionic strength, sodium chloride was added to these solutions when needed. While kept
at a constant temperature, the solutions were treated using two different techniques. They were either
degassed with low CO2 content gas (atmospheric air) or simply just stirred for a certain period of time.
The degassing technique [24] allows obtaining higher super saturation of the Ca-carbonic solutions with
respect to CaCO3. In each run, the evolutions with respect to time of the calco-carbonic solution
properties were followed. The most important tracked parameters were the solution pH and calcium
content. Both are good indicators to spot the exact moment of the occurrence of the CaCO3 nucleation.
Any drop of these parameters reveals the starting of the scaling phenomena.

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IV. RESULTS AND DISCUSSION

The novel index was first checked with some experimental results obtained by bubbling CO2 into an
alkaline solution. For the first set of experiments, the operating conditions are favorable of a calcium
carbonate spontaneous precipitation as shown in Table 1. In the same table are given the ionic strength,
the induction time (tG) and the corresponding solution pH (pHG), super saturations with respect to calcite
(Calcite) and monohydrate (MCC) and the MLSI values. In this set of experiment, the solutions for
which the ionic strength lied between 0.005 and 1.5, were supersaturated not only with respect to calcite
but also with respect to MCC. The MLSI values were all positive which is consistent with the scaling
nature of the solution. It is worthy to note that the induction time decreases almost exponentially as the
MLSI increases. For higher super saturations, ionic strength increase seems to have significantly
different effect on the nucleation kinetic than that for lower super saturations. As shown in Figure 1,
increasing the ionic strength apparently retards the nucleation time for low super saturation. For high
super saturations the effect of salting on the induction time seems to be reversed.

Table 1: MLSI values where spontaneous precipitation took place (T=30C).

Run Solution [Ca2+] [Alc] Ionic
pHG tG (min) Calcite MCC MLSI
Nb. nature (mM) (mM) Strength
01 1.8 3.6 0.0054 8.62 70 27.7 1.4 0.15
02 2 4 0.0060 8.60 64 34.3 1.7 0.21
03 Pure calco- 2.5 5 0.0075 8.67 32 56.0 2.7 0.51
04 carbonic 3 6 0.0090 8.68 22 79.3 3.8 0.61
05 Solutions 4 8 0.0120 8.59 16 108 5.2 0.74
06 5 10 0.0150 8.51 11 135 6.52 0.83
07 4 8 0.0120 8.73 7 147 7.65 0.88
08 3.5 6 0.9 8.82 135 27.7 1.34 0.13
09 4 8 1.5 8.74 124 34.7 1.68 0.22
10 NaCl loaded 4 8 1.0 8.76 82 36.2 1.75 0.24
11 Solutions 4 8 0.8 8.80 52 41.2 1.99 0.30
12 4 8 0.6 8.84 35 48.6 2.35 0.37
13 4 8 0.4 8.80 22 50.9 2.46 0.39
14 4 8 0.2 8.81 13 76.0 3.67 0.56

In the second set of experiments, the solutions were treated for periods ranging from few hours to few
days. No calcium carbonate germination was observed for all the experiments. The operating conditions
as well as the corresponding MLSI and the super saturation values are given in Table 2. Almost all the
reported MLSI values were negative. This indicates that the solutions had a non scaling behavior as no
precipitation occurred despite the relatively long monitoring time. Thus, the MLSI has successfully
predicted the non scaling character of the solutions. The only exception was for run 21 for which the
corresponding MLSI value was slightly positive (0.04). As reported in our previous work this case could
be explained by the experimental error mainly on the pH value. Indeed, when considering that the pH is
fixed within 0.05 along with a relative experimental errors on [Ca] and [Alc] of 2 %, the absolute
uncertainty on the MLSI is approximately 0.05.

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150
Pure Calco-carbonic Sol

NaCl loaded Sol

Induction Time, TG (min)

100

50

0
0,1 1
MLSI

Figure 1: Induction time vs. MLSI values for pure Ca-carbonic and loaded NaCl solutions at 30C.

Table 2: MLSI and supersaturation values for cases where no spontaneous precipitation had occurred.
Solution Ionic T [Ca] [Alc] Monitoring
Run Nb. pH Calcite MCC MLSI
nature Strength (C) (mM) (mM) Time
15 0.003 8.50 1 2 31 days 7.20 0.35 -0.44
16 0.0055 8.50 1.5 3 04 hours 15.2 0.73 -0.12
17 Pure calco- 0.0075 7.90 2.5 5 07 hours 10.0 0.48 -0.27
18 carbonic 0.012 30 7.60 4 8 60 days 11.7 0.57 -0.25
19 Solutions 0.012 7.75 4 8 24 hours 16.5 0.80 -0.10
20 0.012 7.40 4 8 02 days 7.40 0.36 -0.45
21 0.015 7.71 5 10 02,5 hours 22.3 1.08 0.04
22 0.075 25 8.15 10 2 04 hours 12.6 0.61 -0.18
Natural
23 0.075 30 8.05 10 2 06 hours 11.3 0.55 -0.25
Water
*
24 0.075 65 6.8 10 2 Infinite 3.10 0.15 -0.77
25 1.0 25 8.71 2.5 5 26 hours 11.8 0.55 - 0.30
26 NaCl Loaded 0.8 25 8.63 3 6 24 hours 14.6 0.69 - 0.21
calco-
27 1.5 30 8.33 4 8 24 hours 13.5 0.65 -0.19
carbonic
28 Solutions 0.6 30 8.30 4 8 04 hours 14.0 0.68 -0.17
29 1.0 25 8.48 4 8 20 hours 17.7 0.83 -0.12
(*) Case relative to exit conditions of geothermal water, no scaling has occurred.

These non scaling solutions have a low super saturation with respect to calcite and are below saturation
for the MCC (except for run 21). They could be considered as calco-carbonic solutions at equilibrium
especially with the absence of any CaCO3 seeds usually trapped, if present, in the water pretreatment
process in reverse osmosis desalination units.
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IV.1 Comparison of the MLSI to SDSI and LSI

In this section the ability of the MSLI to predict the scaling behavior of water is compared to that of the
SDSI and LSI. The scaling indices of water with various salinities, covering the concentration range of
that of the feed and the reject fluxes of a reverse osmosis desalination unit, are evaluated and compared.
The calculated SI according to the water physico-chemical properties (T, pH, Ca, Alc, ionic strength) and
the monitoring time are reported in Table 3.

Table 3: MLSI, LSI and SDSI values for several water qualities.
Run Solution T Ionic [Ca] [Alc] TDS Monitoring
pH MLSI LSI SDSI
Nb. nature (C) Strength (g.L-1) (g.L-1) (g.L-1) Time
30 1 0.12 0.366 58.56 8.33 22 hours -0.52 1.33 0.16
31 1 0.80 0.244 58.47 8.80 24 hours -0.40 1.50 0,33
25 1 0.100 0.305 58.47 8.71 26 hours -0.30 1.60 0.53
26 0.8 0.12 0.366 46.76 8.63 24 hours -0.21 1.63 0.56
32 25 1 0.12 0.305 58.46 8.75 28 hours -0.18 1.73 0.56
29 1 0.16 0.488 58.45 8.48 20 hours -0.12 1.76 0.64
*
33 1 0.12 0.366 58.46 8.92 180 min 0.07 1.98 0.81
*
34 0.8 0.12 0.366 46.76 8.99 90 min 0.16 2.03 0.96
NaCl *
35 loaded 1 0.16 0.488 58.47 8.90 70 min 0.30 2.21 1.08
36 calco- 0.9 0.14 0.366 52.6 8.54 48 hours -0.15 1.73 0.52
carbonic
37 0.8 0.16 0.488 46.75 8.35 24 hours -0.15 1.17 0.58
Solutions
38 1 0.16 0.488 58.5 8.40 24 hours -0.12 1.81 0.58
28 0.6 0.16 0.488 35.1 8.30 4 hours -0.17 1.64 0.61
27 1.5 0.16 0.488 87.7 8.33 24 hours -0.19 1.75 0.64
30 *
8 0.9 0.14 0.366 52.6 8.82 135 min 0.13 2.04 0.89
*
10 1 0.16 0.488 58.5 8.76 82 min 0.24 2.17 0.99
*
11 0.8 0.16 0.488 46.75 8.80 52 min 0.3 2.19 1.08
*
9 1.5 0.16 0.488 87.7 8.74 124 min 0.22 2.40 1.14
*
12 0.6 0.16 0.488 35.1 8.84 35 min 0.37 2.22 1.20
24 65 6.80 infinite -0.77 0.56 0.36
23 Natural 30 8.05 06 hours -0.25 1.11 1,03
3.1 0.075 0.40 0.122
22 Water 30 8.15 04 hours -0.18 1.22 1,13
39 25 8.20 02 hours -0.18 1.37 1,27
20 0.012 0.16 0.488 7.40 02 days -0,45 0.76 0.94
Pure calco- 0.4
18 0.012 0.16 0.488 7,6 60 days -0,25 0.98 1.16
carbonic 30
17 Solutions 0.25 0.0075 0.063 0.082 7.90 07 hours -0,27 1.07 1.28
19 0.4 0.012 0.16 0.488 7,75 24 hours -0,1 1.13 1.32
(*) Induction time where spontaneous germination took place.

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Most of the imposed conditions are not favorable to scaling (almost 2/3). It is clear that in the
experiments where the scaling took place all the three considered Scaling Indices were capable of
predicting such behavior as their values were positive. In the experiments where no scaling had occurred
even after monitoring the Ca-carbonic solutions for few days, the LSI and SDSI values were positive
ranging between 0.4 and 1.4 and 0.2 and 1.8 for waters of low and high salinities respectively. Both
indices were then capable of predicting the scaling nature of water but not the non scaling behavior. Only
the MLSI was able to predict the non scaling character of the solutions as its values were negative for the
corresponding cases.

Since in the desalination practices, chemicals (acids ...) are usually used to prevent scaling whenever
expected. Given that the amount of added chemicals is related to the likelihood of the scaling phenomena
occurrence which is somehow proportional to the SI, the use of the MLSI instead of the LSI and the
SDSI would eventually lead to a consumption reduction of chemicals in desalination processes.

All the recent work has strengthened the idea that scaling prediction based solely on the calcite form
reveals some weakness and limited understanding of the CO2-H2O-CaCO3 system. The experimental
evidence showed in our previous work and in the present paper has further sustained that CaCO3
spontaneous germination involves necessarily a precursor which is apparently a calcium carbonate
hydrated form. Specifically, the MCC solubility product presents a lower limit for the calco-carbonic
solution IAP to induce a spontaneous CaCO3 precipitation.

Both the LSI and the SDSI consider, either explicitly or implicitly, the apparent solubility product
equilibrium constant of calcite, the most thermodynamically stable CaCO3 form. This explains the
limitation of these scaling indices as well as many other indices used in water desalination practices as
the scaling is related solely to calcite. The MLSI, which embeds the referred thermodynamic aspects of
the CO2-H2O-CaCO3 system, was consistent with the experimental evidence in the case of saline as well
as highly saline waters. This new index can substitute the traditionally used SI (LSI, SDSI ) for scaling
tendency assessment for various water fluxes in the desalination field.

IV.2 Advantages and drawbacks of the MLSI

The MLSI can be comfortably used in reverse osmosis desalination practices for the following reasons:

- The use of acid and chemical to prevent scaling can be reduced.

- There is no chance that a secondary CaCO3 nucleation could take place as the feed water is generally
rigorously pretreated which is sufficient to trap any suspended matter and mainly calcium carbonate
seeds in the sand filtration operation.
- A critical MLSI value can be used for safe practices, to make up for any imprecision in the evaluation
of the water properties and mainly the pH which determines the foremost error on the scaling index.
If not accounted for this may yield, in the case of very low super saturation with respect to MCC, to
cause a scaling tendency. However, even without this secure margin, in the desalination practice the
risk of CaCO3 germination is minor since the induction time is relatively much greater than the water
mean residence time in the reverse osmosis modules (for example for a MLSI of 0.2 the nucleation
time exceeds 60 min). Moreover, the increase of the ionic strength along the desalination modules as
the salinity increases in the reject flux would have a retarding effect on the induction time (Table 1).

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The major drawback of the newly defined scaling index is the use of complex models such as Pitzers
model to estimate the activity coefficient of the ionic species for highly saline water. In the desalination
practice, since the highest concentration levels is usually below 1M much simpler models could be used
to estimate the same parameters in order to obtain the MLSI to assess the scaling tendency. For instance,
for solutions with an ionic strength below 2, the simplified Pitzer model is an alternative for the original
model. The later model neglects the 3rd order interactions as well as the interactions between ions of the
same charge with a little effect on the MLSI calculation. A comparison between the MLSI values
obtained using the original and the truncated Pitzer models is given in Table 4. The differences, given in
the last column of the table, are relatively small. The simplified model actually yields a slightly higher
MLSI values. The discrepancies increase with the ionic strength, but they did not exceed 0.05 which
represents the experimental error. Thus, the simplified Pitzers model could also be used in reverse
osmosis desalination practices.

Table 4: MLSI values obtained using the original and the simplified Pitzer models.
Run Ionic [Ca] [Alc] TDS MLSI
pH MLSI
Nb. Strength (g.L-1) (g.L-1) (g.L-1) Pitzer Simplified Pitzer
10 1 58.5 8.76 0.239 0.281 0.042
11 0.8 46.75 8.80 0.296 0.337 0.041
0.16 0.488
13 0.4 23.35 8.80 0.388 0.427 0.038
14 0.2 11.65 8.81 0.564 0.552 0.013

Although the Pitzer model accounts for ionic interactions of several orders such as those involving
metallic cations with the calco-carbonic system, further investigations are needed. Indeed, some cations
have a considerable effect on CaCO3 nucleation. Particularly, Mg ions are known to slowdown the
scaling phenomena [22] and to favour the formation of aragonite at the expense of other CaCO3 forms
[23]. Furthermore, in industrial systems the solution properties (pH, species concentrations, T ) are
not homogeneous and may vary with the flow hydrodynamics and the mixing pattern as time evolves.
This would add to the uncertainty in evaluating the representative MLSI value for scaling assessment in
such complex dynamic circumstances.

V. CONCLUSION

The prediction of Calcium Carbonate scaling in reverse osmosis desalination processes is not well
understood. The applied Scaling Indices (SI) and models have some limitations that often lead to an over
consumption of chemicals to prevent scaling. In the desalination field, the Langelier Saturation Index
(LSI) and the Stiff and Davis Stability Index (SDSI) are often used to assess the scaling tendency. Since
these indices involve only the thermodynamic data of calcite, the most stable CaCO3 form, they are short
of predicting the Ca-carbonic equilibrium state. Experimental evidence showed in this paper and similar
published work that the CaCO3 scaling involves necessarily a precursor. Apparently the calcium
carbonate hydrated forms and mainly the Monohydrate Calcium Carbonate (MCC) are playing such
role. The MCC solubility product presents a lower limit for the Ca-carbonic solution Ionic Activity
Product (IAP) to induce a spontaneous CaCO3 precipitation. The newly defined SI, that embeds this
thermodynamic aspect of the CO2-H2O-CaCO3 system, and referred to as the Monohydrated Langelier
Saturation Index (MLSI), is able to predict the scaling as well as the equilibrium state of the calco-
carbonic system. The MLSI can comfortably substitute the LSI and SDSI in reverse osmosis
desalination practices with the added benefit of reducing the use of chemicals to prevent scaling.
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IDA World Congress-Maspalomas, Gran Canaria Spain October 21-26, 2007

REF: IDAWC/MP07-081
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