Desalination 204 (2007) 385402

Scale formation in desalination plants: effect of carbon dioxide solubility

Khalid Al-Anezi, Nidal Hilal*
Centre for Clean Water Technologies, School of Chemical, Environmental and Mining Engineering, University of Nottingham, Nottingham, NG7 2RD, United Kingdom Tel. +44 (115) 9514168; Fax +44 (115) 9514115; email: nidal.hilal@nottingham.ac.uk

Received 16 March 2006; accepted 12 April 2006

Abstract Modeling of the release of CO2 in the multi-stage flash distillers requires knowledge of the CO2 solubility in seawater at the conditions prevailing in the system. The evidence from literature is that measurement of the solubility of CO2 in pure water has been extensively studied, whereas that in saline solutions has not. Several studies have investigated the solubility of CO2 in seawater under different temperatures and pressures, but they have not covered the conditions that prevailed in the desalination plants, such as low pressures and high temperatures. In the lowpressure regime (i.e., near atmospheric pressure), the gas solubility can be theoretically estimated by considering the ionic strength and the salting-out parameter. Gas solubility measurements can be made as a function of the seawater temperature and salinity. Fouling in the MSF plants occurs as a result of alkaline scale formation and it is known that the rate of formation of calcium carbonate and magnesium hydroxide in seawater depends on temperature, pH, concentration of bicarbonate ions, rate of CO2 release, concentration of Ca2+ and Mg2+ ions, and total dissolved solids. This review presents an overview of the CO2 solubility in the brine, carbonate equilibria in the seawater and the various correlations used to characterize the CO2-seawater system. Also, some gas solubility equipment has been mentioned. Keywords: CO2 solubility in seawater; Carbonate equilibria; Fouling in the MSF plants; Desalination.

*Corresponding author.

Presented at EuroMed 2006 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 the University of Montpellier II, Montpellier, France, 2125 May 2006.
0011-9164/07/$ See front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2006.04.036

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1. Introduction The multi-stage flash (MSF) procedure is the most common technique for desalination, found mostly in the Middle East countries. The techniques worldwide capacity adds up to about 48% of the total number of bigger plants having a capacity greater than 4,000 m3/d. Among other evaporation techniques, the multi-effect distillation (MED) may be mentioned here, either with vertical or horizontal smooth tubes or doubly fluted tubes. The vapour compression course is very popular for remote locations, resort areas, islands, etc. These two techniques, though not widely used, are promising as far as good water quality, simple application, reliability, and efficiency are concerned. Membrane processes, mainly reverse osmosis (RO), are currently the fastest-growing techniques in water desalination [1,2]. Challenges, however, still exist to produce desalinated water at affordable costs. The presence of dissolved non-condensable (NC) gases in process water is a serious problem in thermal desalination of seawater, which can deteriorate the performance and efficiency of the whole desalination plant, and hence cause a cost increase in most commercial units. Even low concentrations of NC gases can significantly reduce the overall heat transfer coefficient and hence the performance of desalination evaporators. CO2 dissolves in the condensate and lowers its pH value. In the presence of O2, this may cause corrosion of the condenser tubes. Also, the release of CO2 from the evaporating brine in seawater distillers considerably influences , CO2 , H+ and OH ions concentrations of HCO 3 3 in the carbonate system of the brine and thus plays an important role in alkaline scale formation. Furthermore, an accumulation of NC gases may disturb the brine flow through the flash chambers of multi-stage flash (MSF) distillers. Most often neither a deaerator nor a decarbonator is provided to alleviate the problem of NC gases that is caused by the leakage of ambient air through flanges, man-holes, instrumentation nozzles, etc. into the

parts of the evaporator operating under vacuum and the release of dissolved gases from the evaporating brine. Molecularly dissolved gases such as O2, N2 can be removed by adequate venting. In contrast to that, CO2 chemically reacts in seawater and is produced during the desalination process itself. Under the alkaline conditions prevailing in seawater only a small proportion of the total inorganic carbon content in seawater is present as molecular CO2, the major proportion is chemically and CO2 ions [37]. combined in HCO 3 3 Literature data regarding solubility of CO2 in different solvents and combinations thereof are rather abundant. However solubility in saline water at or near conditions prevailing in the thermal desalinations processes is lacking. Thus, considerable uncertainty exists in predicting the total CO2 absorption or release rates in distillers. This study is essentially aimed at reviewing the solubility of CO2 in the saline water under the conditions prevailing in the multi-stage flash evaporators, since the solubility of CO2 in brine is an important parameter for modelling the behaviour of CO2, especially on the production of the alkaline scales. 2. Theory: CO 2 solubility in seawater and carbonate equilibria The carbonate system is a weak acidbase system which exists in seawater as dissolved carbon dioxide, carbonic acid, bicarbonate, carbonate ions and complexes of these ions. Basically the system is derived from the dissolution of carbon dioxide gas and carbonate minerals into the water. Addition of an acid or a base to an aqueous solution of carbonate species gives rise to changes in pH and changes in the concentrations of all the species that constitute the system. A distinguishing feature of the carbonate system is that the gas phase forms an integral part of it. For a system initially in equilibrium, any change in the partial pressure of CO2 in the gas phase induces a state of non-equilibrium between gas and aqueous phases. This causes, with time, an exchange of CO2 between the phases

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resulting in a shift in pH and the species concentrations until equilibrium between the phases is re-established. A further feature is the relative insolubility of many carbonate minerals; the precipitation and dissolution of these minerals have a significant effect on the systems behaviour. As a consequence of these two features it is often necessary to consider all three phases, aqueous, gas and solid, in order to describe the response of the system to external influences [811]. Seawater is an aqueous mixed electrolyte. It attains its chemical composition through a variety of chemical reactions and physicochemical processes. Among these are: acidbase reactions, gas absorption and desorption processes, precipitation and dissolution of solids and adsorption processes at interfaces. Characteristic for seawater is the high salinity that may vary between average limits of 7 g/kg (Baltic Sea) and 43 g/kg (Arabian Sea). The pH of seawater is usually in the range from 7.7 to 8.3 in surface waters. The pH is buffered by a set of reactions that take place between CO2 and water. Table 1 shows the composition of standard seawater with a salinity of 35 g/kg [7, 12 15].

Many investigators such as [69,13,14,16,17] have given an overview of the carbonate system in seawater and they have summarized the following: the solubility of CO2 in seawater, the chemical equilibria, the mechanisms, the orders and the rates of reactions involved in CO2 release. Also, they described the effects of temperature, pressure and ionic strength on the solubility, the chemical equilibria and the reaction rates. The solubility of CO2 in seawater occur as a result of a number of reactions taking place when carbon dioxide dissolves in seawater [9,12,15,18]. In the presence of gaseous CO2, The dissolved CO2 exchanges with CO2 gas can be represented by series of equilibria. Henrys law describes only the physical equilibrium between the phases and may only be applied to the fraction of the gas that is molecularly dissolved and not chemically bound [1924]. Henrys law coefficient depends on the type of the gas and the solvent, the temperature, the total pressure, and in the case of salt solutions, it also depends on the ionic strength of the solution. Gas solubilities in salt or electrolyte solutions are usually smaller than the gas solubility KG,o in pure water (salting-out effect). The effect of the

Table 1 The composition of standard seawater with S = 35 g/kg, TA = 2.3103 mol/kg and pH = 8.1 at 25C
Species Na Mg2+ Ca2+ K+ Sr2+ Cl SO2 4 HCO3 Br CO2 3 B(OH)4 F B(OH)3 Total
+

Concentration (g/kg seawater) 10.7838 1.2837 0.4121 0.3991 0.0079 19.3529 2.4124 0.1070 0.0672 0.0161 0.0079 0.0013 0.0193 35.1707 (mol/kg seawater) 0.46907 0.05282 0.01028 0.01021 0.00009 0.54588 0.02824 0.00175 0.00084 0.00027 0.00010 0.000068 0.00031 1.1199

Specific concentration (g/kg)/s 0.30811 0.036678 0.01177 0.01140 0.000227 0.55294 0.07750 0.00306 0.00192 0.000459 0.000225 0.000037 0.000551 1.004877

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molar salt concentration cs can be described in the form of the Setchenow equation [25]. Danckwerts [20] related the Henrys law coefficient in the salt solution to that in water at the same temperature on the basis of a method originally proposed by Setchenow [12]. Furthermore, the activity coefficient of CO2 in seawater can be considered as the ratio of its solubility in water to the solubility in seawater. The application to the solubility of CO2 in seawater has lead to the formulation of an empirical correlation which is shown elsewhere [2628]. Yasunishi and Yoshida [29] determined the solubility of CO2 in aqueous solutions of 16 electrolytes and found that the empirical Setchenow equation was not applicable to some electrolyte systems. But [2628] presented an empirical model for the prediction of gas solubilities in electrolyte solutions which described the data with greater accuracy, the observed influence of the salt type on the gas specific part of the Setchenow constant was considered in their model. The model presented by Schumpe [27] has a simple structure and is consistent when applied to mixed electrolyte solutions. The parameter values evaluated for this model allowed estimation of the effects of 20 cations and 19 anions on the solubilities of 15 gases including CO2, further work was carried out by Weisenberger and Schumpe [28] to study the effect of temperature on the model and they extended the model to the temperature range of 273363 K, and assumed that the gas-specific constant to be linear function of the temperature. This model was used to evaluate the Setchenow constants for different gas/salt/temperature combinations in the range of 273363 K, and they observed linear decrease of the Setchenow constant with temperature in most cases. The ionic strength can be related to salinity S and, as it is know, NaCl is the main constituent of seawater and it accounts for 73% of seawater ionic strength, the ion specific parameters of Na+ and Cl are the only considered parameters. Teng et al. [22] presented a theory of CO2-gas

solubility in seawater, and in their paper they investigated the CO2water binary system and CO2-gas solubility in seawater. They carried out a complete mathematical derivation of the CO2 water binary system and CO2-gas solubility in seawater and they have obtained an expression to calculate the solubility coefficient for the CO2water binary system and CO2-gas solubility in seawater similar to that obtained by Weiss [30]. The solubility of CO2 in seawater was measured in [30 33]. The latter work of Weiss [30] supported the accuracy of the measurements of Li and Tsui [31] and led to the formulation that is used to calculate Henrys law constant, Ko for seawater as a function of salinity (S) and temperature (T, K). This equation is derived from the integrated vant Hoff equation and the logarithmic Setchenow salinity dependence, and has the form given by Weiss [30]:
ln K 0 = 60.2409 + 93.4517 (100 / T )

+23.3585ln (T /100 ) + S [ 0.023517

(1)

0.023656 (T /100 ) + 0.0047036 (T /100 )

All of these measurements were made on acidified seawater equilibrated with pure CO2, and with a certain temperature range and salinity range (T = 040oC and S = 040). The extrapolation of Eq. (1) for higher temperatures and salinities does not give reliable results. The more recent measurements of Roy et al. [34] indicate that the Ko measurements by Weiss [30] are consistent with their KoK1 measurements to 0.0003 in log Ko. Since the extrapolation of Eq. (1) for higher temperatures and salinities does not give reliable results, many researchers such as Glade and Genthner [5] determined Henrys law coefficient of CO2 in the brine by using Eq. (5) and using the correlation for Henrys law coefficient in pure water given by Plummer and Busenberg [35] which is valid up to 334oC:

ln KG ,0 = 108.3865 + 0.01985076 T 6919.53T 40.45154 log T + 669365/ T 2

(2)

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However, Duan and Sun [36] proposed a more recent thermodynamic model for the solubility of carbon dioxide in pure water and in aqueous NaCl solutions for temperatures from 273 to 533 K, for pressures from 0 to 2000 bar. Their CO2 solubility model was based on the equation of state (EOS) of Duan et al. [37] and the theory of Pitzer [38,39]. Duan and Suns [36] model was able to predict CO2 solubility in seawater-type brine and was compared to experimental data obtained by Murray and Riley [32] with great accuracy (only 3% deviation from the experimental data). But, this model relies on a complex virial EOS that needs to be solved iteratively. Solubility of gases in the seawater is a function of their molecular weight, temperature and salinity, Table 2 [6,15] shows the concentrations of the gases dissolved in seawater with a salinity of 35 g/kg in equilibrium with the atmosphere at 25C and from this table we can see that CO2 is more soluble than O2, N2 and Ar. The Henrys law coefficient of CO2 decreases with increasing temperature passes through a minimum at 170C and increases again. The Henrys law coefficient also decreases with increasing salinity. The effect of salinity is less pronounced at high temperatures. The dissociation of H2CO3 in water, the dissociation of water obeys the equilibrium conditions and are important parts of carbonic acid equilibria [9,12,15,18], where the equilibrium conditions are quantified by the dissociation or acidity constants:
K1 = [H+ ][HCO3 ]/[H 2 CO3 ]

and
2 K 2 = [H + ][CO3 ]/[HCO3 ]

(4)

H 2 O H+ + OH , where KW = [H + ][OH ] (5)

The carbonate system in seawater is characterised by the interaction of major cations (Na+, , Mg2+, Ca2+ and K+) and major anions (Cl, SO2 4 2 and CO ). These interactions can be deHCO 3 3 scribed in terms of an ion association formalism and, more recently, in terms of a specific interaction theory [6,12,13,15,40].
2 Na + + CO3 NaCO3 , + Ca 2+ + HCO3 CaHCO3 ,

(6)

Mg 2+ + OH MgOH +
2 + H + + SO4 HSO 4 , H + F HF

(7)

Additionally insoluble calcium carbonate and magnesium hydroxide can be formed [41,42]. Fig. 1 was presented by Al-Rawajfeh [12] and it shows a schematic representation of the carbonate system in gas, liquid and solid phases. The dissociation constant of water, the stoichiometric equilibrium constant of water in seasw can be expressed as: water Kw
sw sw sw Kw = Kw / H = [H + ]sw [OH ]sw + OH

(8)

(3)

Culberson and Pytkowicz, Dickson and Riley, Hansson and Mehrbach et al. [4346] measured

Table 2 Solubility data of the gases dissolved in seawater with S = 35 g/kg in equilibrium with the atmosphere at 25C
Gas CO2 N2 O2 Ar Partial pressure in atmosphere (bar) 0.00033 0.7808 0.2095 0.00934 Henrys law coefficient (mol/(m3bar)) 29.3 0.5 1.0 1.1 Concentration in seawater (mol/kg SW) 9.45 383.4 206.3 10.11 (mg/kg SW) 0.4 10.7 6.6 0.4

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Fig. 1. Schematic representation of the carbonate system.

the equilibrium constant of water in seawater for temperatures up to 35C and salinities up to 44 g/kg. Another correlation to calculate the equilibrium sw can be found in constant of water in seawater Kw another reference [44]. Basically all values of the solubilities and dissociation constants are temperature dependent. However, the K values also depend on the solute concentrations, because the formation of ion complexes between the carbonic ions and molecules and ions in the solution hinder the dissolved carbonic molecules and ions to take part in the thermodynamic equilibrium reactions. Therefore, in the thermodynamic equation, the concentrations have to be replaced by their activities that are smaller than the concentrations. The thermodynamic solubility constant is:
K o = a [H 2 CO3 ]/ PCO2

bilities and dissociation constants can sited elsewhere [6,9,11,17,47]. For practical reasons the values of the dissociation constants are generally given as: pK = 10log K or K = 10pK. Many investigators as in [34,44 46,4851] presented various correlations of the dissociation constants K1sw and K2sw of carbonic acid in seawater. Millero [7], Lueker et al. [47], Millero et al. [52] investigated the parameters used to study the carbonate system such as pH, total alkalinity (TA), fCO2 (fugacity) and TCO2, since a combination of at least two of these parameters is needed to characterise the carbonate system. Millero [7] suggested two correlations for calculating the stoichiometric dissociation constants K1sw and K2sw and these correlations are based on the experimental data of [34,49]:
ln K1sw = 2.18867 2275.036/ T 1.468591ln T + ( 0.138681 9.33291/T ) S 0.5 (10) + 0.0726483S 0.00574938S1.5
sw ln K 2 = 0.84226 3741.1288/ T

(9)

where, in general, the activity coefficients >1 ( = 1 for an ideal solution, i.e. with zero solute concentrations or zero ionic strength). In the non-ideal solutions of seawater and brackish water it is more practical to describe the relation between the real, measurable concentrations by the apparent solubility constant. Full details of the correlations to calculate the solu-

1.437139ln (T ) + ( 0.128417 24.41239 / T ) S 0.5 + 0.1195308S 0.00912840 S 1.5

(11)

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where K 1sw and K 2sw are on the basis mol/kg seawater, T is in K and S is in g/kg. Figs. 26 show the solubility constants (= solubilities in M/L.atm) and stoichiometric dissociation constants K1sw and K2sw for CO2 in freshwater, seawater and brackish water as a function of temperature and salinities. 3. Fouling, alkaline scale formation and solubility product of calcium carbonate Fouling is the accumulation of undesired solid materials at the phase interfaces. Build-up of fouling film 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. Alkaline scale formation in seawater distillation begets from the decomposition hydrolysis of seawater bicarbonate ion as process temperature is increased [53]. In real-life situations, scale deposits are formed mainly through thermal effects. In fact, heating of the water has the consequence that carbon dioxide solubility decreases, pH increases and finally calcium carbonate precipitates. Multi-stage flash (MSF) plants usually operate at temperatures as high as 120C, and multiple effect evaporation (MED) plants operate at temperatures lower than 70C. Consequently, the major risk of scaling is for minerals whose solubility decreases with increasing temperature. The mostly

Fig. 2. The solubility constants (= solubilities in M/L.atm) for CO2 in freshwater, seawater and brackish water as a function of temperature at salinities of 0, 5, 15, 25, and 35 (= g of salt per kg of water) (upper graph) and as a function of salinity at 20C (lower graph). All values are according to [7, 88], at higher salinities similar to [30] [Eq. (7)]; the values for freshwater are similar to those in [89].

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Fig. 3. The acidity constants for the first dissociation of carbonic acid in freshwater and seawater as a function of the water temperature at salinities of 0, 5, 15, 25, and 35. The values are according to [7,88]. The freshwater values are equal to those in [89], the marine values are in good agreement with those reported in [46] as discussed in [48].

observed scales that occur in MSF distillers are found to be either CaCO3 or Mg(OH)2. The two are commonly referred to as alkaline scale. The formation of the alkaline scales CaCO3 and Mg(OH)2 strongly depends on temperature, pH, the release rate of CO2 as well as the concentra, CO2 , Ca2+, and Mg2+ ions. Lots of tions of HCO 3 3 metals and anions exist naturally in the water; among them, CaCO3 and CaSO4 are major fouling contributors [2,4,5461]. Al-Sofi [4] made an attempt based primarily upon visual and reported observations of fouling in various parts along the flow path of brine solutions in MSF distillers and proposed a certain sequence of scale forming reaction steps, and also suggested certain experiments that could verify the validity of his proposed reaction mechanism. Meanwhile, the presence of hydroxyl ions will

be short lived primarily due to Mg(OH)2 precipitation. The proposed steps support CaCO3 precipitation ahead of Mg(OH)2. The abundance of magnesium ions and the extreme low solubility of magnesium hydroxide will then rapidly lead to its formation. However, scale precipitation inside tubes is not only from the initial scale formation under pressure inside the tubes but also due to nucleates recirculation from flash chambers back into heat gain exchanger tubes because of brine recycling. Recent analysis of variation in coloration of water boxes came as a strong support to this hypothesis. It is worth to note that the end results of various reaction mechanisms are almost the same in the cited ones also the same to the proposed overall reaction. A number of studies done by Al-Rawajfeh [3, 12] Shams El Din and Mohammed [42], Al-

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Fig. 4. The acidity constants for the second dissociation of carbonic acid in freshwater and seawater as a function of the water temperature at salinities of 0, 5, 15, 25, and 35. The values are according to [88]. The freshwater values are equal to those in [89], the marine values are in good agreement with those reported in [46] as reported in [48].

Rawajfeh et al. [62] to analyze scale formation in seawater distillers which is mainly caused by crystallization of the inversely soluble salts calcium carbonate, magnesium hydroxide, and calcium sulphate. The release of CO2 from the evaporating brine shifts the pH to higher values and considerably influences the concentrations of HCO 3 and CO2 ions in the brine. Thus, it plays an im3 portant role in alkaline scale formation. CO2 release and alkaline scale formation in seawater distillers are closely related to the carbonate system in the brine. Al-Rawajfeh [3] proved that the model developed by Al-Rawajfeh [3,12,18,58,62] is very useful to calculate the CO2 release rates , CO2 , CO2, H+ and OH concentraand the HCO 3 3 tions in the brine on its flow path through multipleeffect distillers. A simple and easy programmed code is pro-

posed by Al-Shammiri et al. [63] for estimating the scaling potential for different scaling species that expected to be precipitated in an RO system, as calcium carbonate, calcium sulfate, barium sulfate, calcium fluoride and strontium sulfate scaling. Azaroual et al. [64] presented a thermokinetic geochemical calculation program (SCALE2000) based on Pitzers ion interaction model, which can take into account the fluid flow effect using a specific approach based on a scheme of serially connected homogeneous reactors. According to the authors [64,65] SCALE2000 is well adapted to perform scaling risk prediction applied to industrial desalination facilities and the authors tested the reliability of the SCALE2000 results against measurements of individual mineral solubility and kinetics data derived from the literature.

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Fig. 5. Values for the first and second dissociation constants of dissolved carbonic acid as a function of the salinity. The values are valid for a water temperature of 20C. Values for the first and second dissociation constants of dissolved carbonic acid as a function of the salinity [7,88].

Fig. 6. Distribution of the carbonic acid fractions as a percentage of the total carbon content, CT. The values are calculated at temperatures of 5 and 25C and for salinities of 0 and 35 as a function of the pH. Seawater has pH values around 8.2. However, the carbon distributions are shown for an (unrealistic) wider range of pH values, to illustrate the dependence of the carbon distribution on salinity [7,88,90].

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Calcium carbonate CaCO3 dissolves according to the following equation:

2 CaCO3(S ) Ca 2+ + CO 3

(12)

The solubility product of calcium carbonate is given by

sw sw sw 2 sw K sp = K sp / Ca = [Ca 2+ ]sw [CO3 ] 2+ CO 2
3

(13) where Ksp is the thermodynamic solubility product are the concentration and the and [i]sw and sw i activity coefficients of the component i, respectively. sw of calcite and aragonite, respectively, can Ksp be calculated from correlations reported by Dickson and Millero [48], Sheikholeslami and Ong [61], Azaroual et al. [64], Mucci [66], Zuddas and Mucci [67] for a salinity between 5 and 45 g/kg and a temperature between 5 and 40C at 1 atm sw values increase with pressure total pressure. Ksp and salinity but decrease with temperature. At T = 30C, S = 60 g/kg and p = 10 bar, the values of

sw , Ksw and Kw differ from the values at 1 bar by Ksw 1 2 sw differs 1%, 0.3% and 0.3%, respectively [8]. Ksp from the values at 1 bar by 0.3%. Thus, for small and moderate pressures, the pressure dependence of the equilibrium constants can be neglected. The activity coefficients in reality are complex functions of the composition of the aqueous solution. In electrolyte solutions, the activity coefficients are influenced mainly by electrical interactions. Much of their behaviour can be correlated in terms of the ionic strength defined by:

I=1

zi2 mi

(14)

In general, model equations which express the dependence of activity coefficients on solution composition only in terms of the ionic strength are restricted in applicability to dilute solutions. Al-Rawajfeh, [12] has summarised the theoretical expressions for the activity coefficients in Table 3 [6,8,19,25,6872]. Many researchers such as Al-Rawajfeh [12] and Mucci [65] have used the Davies equation to

Table 3 Expressions for activity coefficients with zi as the charge of the ion, A as the DebyeHckel parameter which depends on the dielectric constant of the solvent and on the temperature; for water at 25C A = 0.509 kg1/2 mol1/2; B as temperaturedependent parameter; ai and bi as ion specific parameters
Approximation DebyeHckel Extended DebyeHckel Equation Applicability
2 i

log i = Az

I I 1 + Bai I I 1 + Bai I + bi I

I < 0.005 mol/kg I < 0.1 mol/kg

log i = Azi2 log i = Azi2

WATEQDebyeHckel

I < 1 mol/kg

Davies

log i = Azi2

1+ I

0.2 I

I < 0.5 mol/kg I < 0.1 mol/kg useful for mixed electrolytes

Gntelberg

I log = Az 2 i i 1+ I

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K. Al-Anezi, N. Hilal / Desalination 204 (2007) 385402 Table 4 Activity coefficients for some species in seawater (S = 35 g/kg) at 25C
Species Activity coefficient in seawater (I = 0.72 mol/kg) Loewenthal and Marais Na Ca2+ HCO 3 Cl CO2 3 CO2
+

describe the concentration dependence of activity coefficients:

log i = A zi2

( I / (1 + I )) 0.2I

(15)

It should be noted that many other workers have replaced the value of 0.2 with 0.3 value. The Davies equation is normally only used for temperatures close to 25C. It is only accurate up to ionic strengths of a few tenths molal in most solutions. With zi as the charge of the ion Helgeson and Kirkham [73] presented an interpolation formula to calculate the DebyeHckel constant A:
A = 0.4819 + 0.0011T

Davies equation 0.69 0.23 0.69 0.69 0.23

0.693 0.248 0.669 0.649 0.203 1.17 1.167

(15a)

where T is the temperature in C, which is valid for I < 0.5 mol/kg, has the advantage that it needs no adjustable ion size parameter. Davies Eq. (15) is used in many of the chemical equilibrium systems because of its simplicity. In this version of DebyeHckel equation a simple term, linear in I, was added at the end of the equation. This term improves the empirical fit to higher ionic strength but it has no theoretical justification [12,65,72,74,75]. The activity coefficients for seawater (I = 0.72 mol/kg) are for monovalent ions i = 0.69, for divalent ions i = 0.23 and for trivalent ions i = 0.04 (Table 4). Loewenthal and Marais [11] concluded that these values are realistic even though seawater ionic strength is outside the valid range of this equation. 4. Carbonate system and chemical kinetics The carbonate system in seawater have been described in [6,7,9,51,52,58,7678] by the following six quantities: 1. Concentration of dissolved CO2 [CO2]. ]. 2. Concentration of bicarbonate ions [HCO 3 ]. 3. Concentration of carbonate ions [CO2 3 4. pH value or concentration of H+ ions [H+] or concentration of OH ions [OH]. For seawater samples, three pH scales have been proposed

(seawater scale, total proton scale, and free proton scale [7981]). 5. Total carbon dioxide content, TC:
2 TC = [HCO3 ] + [CO3 ] + [H 2 CO3 ]

(16)

6. Total alkalinity, TA. The alkalinity is a practical quantity, following from the conservation of electroneutrality in solutions where the metal ion concentrations (Na, Ca, Mg) and pH are constant, the concentration of all bases that can accept a proton when seawater is titrated to the pH end point of carbonic acid:
2 TA = [HCO3 ] + 2 [CO3 ] + [OH ] [H + ]

+ [other weak acid atoms]

(17)

in which concentrations of other weak acids may be included in the interest of high precision, such ], as humic acids in freshwater or borate, [B(OH) 4 in seawater. Alkalinity and total carbon dioxide are both conservative properties (i.e. salinity is conservative). Stumm and Morgan [40] related the total alkalinity TA to chlorinity, Cl, and it is known that TA and TC vary as a result of any changes in salinity due to mixing, evaporation or dilution, so, to remove these variations Millero et al. [17] presented the normalized values NTA and NTC which are defined as follows:

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NTA = TA X ( 35/ S )

(18)

and
NTC = TC X ( 35 / S )

(19)

with NTA, NTC, TA and TC in mol/kg and S in g/kg. Many authors [6,8,33,8284] have described the reaction mechanisms and reaction rates of the hydration and dehydration of CO2 in aqueous bicarbonatecarbonate solutions. They have presented parallel reaction mechanisms and presented many correlations to calculate the reaction rate constant and reaction time. In our study of the solubility of CO2 in seawater we will be using these reaction mechanisms to determine the reaction rates, reaction time and the rate constants since it is known that the reaction rate depends on the temperature, the pressure and the ionic strength. 5. Vaporliquid equilibrium and gas solubility apparatus previously used Many researchers have tested different types of experimental equipment to measure the gas solubility in alkaline and saline solutions under different experimental conditions. Yasunishi and Yoshida [29] and Tokunaga [85] used an apparatus that was comprised of an absorption chamber, gas burettes, manometer and a stirrer of magnet coated with glass in it. They determined the solubility of CO2 in aqueous solutions of 16 electrolytes by using the gas volumetric method at 1 atm and temperatures of 15, 25, and 35C. They evaluated the CO2 solubilities by the Ostwald coefficient, L and concluded that the empirical Setschenow equation was not applicable to some systems. The data of those systems were correlated by a two-parameter equation within a deviation of 2%. A bubble column reactor has been designed by Shorter et al. [86] to study the uptake of gas in liquid, and they concluded that this technique had an applicability wider than the deter-

mination of solubilities and simple reaction rates. The device, for example, has a unique utility in studying interactions at the gasliquid interface. Researchers such as Lueker et al. [47] designed an apparatus that consisted of an equilibrator and vacuum extraction system to achieve complete and stable thermodynamic equilibrium of CO2 between the gas and solution phases in a closed system and to provide for sampling of the gas and solution without disturbing the equilibrium. The partial pressure of carbon dioxide in the oceans surface waters, precisely expressed as the fugacity fCO is determined from dissolved inorganic carbon 2 DIC and total alkalinity TA. A PVT apparatus was designed by Nighswander et al. [87] where they employed a technique for liquid sample withdrawal, which was shown to provide accurate and reproducible gas solubility measurements at temperatures up to 200C and pressure up to 10 MPa. They found that CO2 solubility is slightly lower in a 1 wt % NaCl solution than in pure water due to the saltingout effect. It is clear from the previous studies conducted on the CO2 solubility in alkaline solutions that there are many more different designs of gas solubility equipments that have been used for the measurement of CO2 absorption in alkaline and saline solutions. If a study of CO2 solubility is to be carried out for conditions similar to those in MSF plants, careful consideration should be taken into account for the effect of temperature, pressure, salinity, and pH. 4. Conclusions The resulting survey of the literature has shown that there are different models to measure the solubility of CO2 in seawater under different conditions, and many workers have suggested certain reaction mechanisms trying to better understand the reaction kinetics that takes place in these conditions. Generally, the solubility of a gas in water decreases as the water warms, and it is known

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that high temperature conditions are usually encountered in desalination plants. Due to high temperatures encountered in the desalination plants, pH rise caused by the carbon dioxide loss involves calcium carbonate precipitation. In MSF desalination plants fouling occurs as a result of CO2 release and alkaline scale formation in seawater distillers. Therefore, there is a need for in-depth knowledge of solubility of CO2 in seawater. Acknowledgements We would like to thank The Public Authority of Applied Education in Kuwait (PAAET) for funding this work. Symbols A aq ci Cl g h DebyeHckel constant Dissolved phase Concentration of the ion i, kmol/m3 Chlorinity, g/kg Gaseous phase Summation of ion specific parameters of the positive ions (h+), negative ions (h) and the gas specific parameter (hG) Ion-specific parameter, m3/kmol Gas-specific parameter, m3/kmol Gas-specific part of the Setchenow constant, m3/kmol Ionic strength, mol/kg First dissociation or acidity constants Second dissociation or acidity constants Thermodynamic equilibrium constant of water Stoichiometric equilibrium constant of water in seawater, mol/kg seawater Gas solubility coefficient in salt solution, mol L1 atm1 or moles kg1 atm1

Gas solubility in water, moles kg1 atm1 KG,o/KG Ratio of the gas solubility in water to that in a salt solution mi Molality of ion i ni = ci / cs Index of ion i Atmospheric CO2 partial pressure, PCO 2 PCO , atm 2 S Salinity of the seawater, g/kg T System temperature, C or K TA Total alkalinity, mol/kg TC Total carbon dioxide content Charge of ion i zi Concentration of the component i [i]sw [H2CO3] Dissolved CO 2 concentration in mol/kg of water Greek sw CO isw
2

KG,o

Activity coefficient of carbon dioxide Activity coefficient of the component i that is free or involved in ion pairing

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