Desalination 204 (2007) 385–402

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, 21–25 May 2006.
0011-9164/07/$– See front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2006.04.036

The vapour compression course is very popular for remote locations. and efficiency are concerned. however. bicarbonate. the major proportion is chemically and CO2– ions [3–7].000 m3/d. Basically the system is derived from the dissolution of carbon dioxide gas and carbonate minerals into the water. Even low concentrations of NC gases can significantly reduce the overall heat transfer coefficient and hence the performance of desalination evaporators. Challenges. Introduction The multi-stage flash (MSF) procedure is the most common technique for desalination. In the presence of O2. These two techniques. N. 2. Thus. man-holes. 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. A distinguishing feature of the carbonate system is that the gas phase forms an integral part of it. mainly reverse osmosis (RO). which can deteriorate the performance and efficiency of the whole desalination plant. 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. an accumulation of NC gases may disturb the brine flow through the flash chambers of multi-stage flash (MSF) distillers. CO2 chemically reacts in seawater and is produced during the desalination process itself. the multi-effect distillation (MED) may be mentioned here. are promising as far as good water quality. combined in HCO– 3 3 Literature data regarding solubility of CO2 in different solvents and combinations thereof are rather abundant. etc. Hilal / Desalination 204 (2007) 385–402 1. etc. the release of CO2 from the evaporating brine in seawater distillers considerably influences . In contrast to that. CO2 dissolves in the condensate and lowers its pH value. For a system initially in equilibrium. This causes. carbonic acid. and hence cause a cost increase in most commercial units. especially on the production of the alkaline scales. 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. 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. found mostly in the Middle East countries. resort areas. Also. Membrane processes. considerable uncertainty exists in predicting the total CO2 absorption or release rates in distillers. CO2– .2]. with time. carbonate ions and complexes of these ions. this may cause corrosion of the condenser tubes. are currently the fastest-growing techniques in water desalination [1. any change in the partial pressure of CO2 in the gas phase induces a state of non-equilibrium between gas and aqueous phases. Furthermore. Among other evaporation techniques. an exchange of CO2 between the phases . instrumentation nozzles. reliability.386 K. 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. simple application. N2 can be removed by adequate venting. Under the alkaline conditions prevailing in seawater only a small proportion of the total inorganic carbon content in seawater is present as molecular CO2. either with vertical or horizontal smooth tubes or doubly fluted tubes. However solubility in saline water at or near conditions prevailing in the thermal desalinations processes is lacking. Al-Anezi. The presence of dissolved non-condensable (NC) gases in process water is a serious problem in thermal desalination of seawater. though not widely used. islands. Theory: CO 2 solubility in seawater and carbonate equilibria The carbonate system is a weak acid–base system which exists in seawater as dissolved carbon dioxide. The technique’s worldwide capacity adds up to about 48% of the total number of bigger plants having a capacity greater than 4. still exist to produce desalinated water at affordable costs. since the solubility of CO2 in brine is an important parameter for modelling the behaviour of CO2.

The pH is buffered by a set of reactions that take place between CO2 and water.K.4124 0. Table 1 shows the composition of standard seawater with a salinity of 35 g/kg [7. The dissolved CO2 exchanges with CO2 gas can be represented by series of equilibria.1199 Specific concentration (g/kg)/s 0.12.000037 0.18]. Many investigators such as [6–9.2837 0.3×10–3 mol/kg and pH = 8.01028 0.30811 0.00084 0.14.00027 0.02824 0.00175 0.54588 0. the mechanisms. precipitation and dissolution of solids and adsorption processes at interfaces.o in pure water (salting-out effect).3991 0. Al-Anezi.01177 0.4121 0.7838 1. Hilal / Desalination 204 (2007) 385–402 387 resulting in a shift in pH and the species concentrations until equilibrium between the phases is re-established. It attains its chemical composition through a variety of chemical reactions and physicochemical processes.17] have given an overview of the carbonate system in seawater and they have summarized the following: the solubility of CO2 in seawater.1707 (mol/kg seawater) 0.036678 0.3529 2.05282 0.00010 0.0079 0. gas and solid.7 to 8. TA = 2. The effect of the Table 1 The composition of standard seawater with S = 35 g/kg. 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.00031 1. Also. the orders and the rates of reactions involved in CO2 release. Henry’s 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 [19–24].1070 0. N. the chemical equilibria and the reaction rates. the temperature.0161 0.000068 0. and in the case of salt solutions.000227 0.00009 0. in order to describe the response of the system to external influences [8–11].00192 0. the chemical equilibria.0193 35. aqueous.000551 1. the total pressure. Seawater is an aqueous mixed electrolyte. 12– 15].004877 . As a consequence of these two features it is often necessary to consider all three phases. they described the effects of temperature.01140 0. 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).46907 0.15.1 at 25°C 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) 10.3 in surface waters.55294 0. the precipitation and dissolution of these minerals have a significant effect on the system’s behaviour.000225 0.01021 0. In the presence of gaseous CO2. A further feature is the relative insolubility of many carbonate minerals. Among these are: acid–base reactions. pressure and ionic strength on the solubility. Henry’s law coefficient depends on the type of the gas and the solvent.00306 0. The solubility of CO2 in seawater occur as a result of a number of reactions taking place when carbon dioxide dissolves in seawater [9.07750 0.13.0672 0. The pH of seawater is usually in the range from 7.16.000459 0.0079 19. gas absorption and desorption processes.0013 0.

the activity coefficient of CO2 in seawater can be considered as the ratio of its solubility in water to the solubility in seawater. and they observed linear decrease of the Setchenow constant with temperature in most cases. K). Since the extrapolation of Eq. 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 CO2.53T − 40. Danckwerts [20] related the Henry’s 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].01985076 × T −6919. and assumed that the gas-specific constant to be linear function of the temperature.3585ln (T /100 ) + S ‰ [ 0. (1) for higher temperatures and salinities does not give reliable results.023656 (T /100 ) + 0. (5) and using the correlation for Henry’s law coefficient in pure water given by Plummer and Busenberg [35] which is valid up to 334oC: ln KG . The application to the solubility of CO2 in seawater has lead to the formulation of an empirical correlation which is shown elsewhere [26–28]. Teng et al. Furthermore.2409 + 93. the observed influence of the salt type on the gas specific part of the Setchenow constant was considered in their model. The more recent measurements of Roy et al. and has the form given by Weiss [30]: ln K 0 = −60.388 K. and in their paper they investigated the CO2–water binary system and CO2-gas solubility in seawater. and with a certain temperature range and salinity range (T = 0–40oC and S ‰ = 0–40).45154 × log T + 669365/ T 2 (2) .0003 in log Ko. The ionic strength can be related to salinity S and. Al-Anezi.0047036 (T /100 ) All of these measurements were made on acidified seawater equilibrated with pure CO2.0 = 108. [34] indicate that the Ko measurements by Weiss [30] are consistent with their KoK1 measurements to ±0. many researchers such as Glade and Genthner [5] determined Henry’s law coefficient of CO2 in the brine by using Eq. 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. 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 273–363 K. The model presented by Schumpe [27] has a simple structure and is consistent when applied to mixed electrolyte solutions.023517 (1) −0.4517 (100 / T ) +23. NaCl is the main constituent of seawater and it accounts for 73% of seawater ionic strength. 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 CO2–water binary system and CO2-gas solubility in seawater similar to that obtained by Weiss [30]. The extrapolation of Eq. But [26–28] presented an empirical model for the prediction of gas solubilities in electrolyte solutions which described the data with greater accuracy. [22] presented a theory of CO2-gas solubility in seawater. N. 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 Henry’s law constant. Hilal / Desalination 204 (2007) 385–402 molar salt concentration cs can be described in the form of the Setchenow equation [25]. (1) for higher temperatures and salinities does not give reliable results. the ion specific parameters of Na+ and Cl– are the only considered parameters. The solubility of CO2 in seawater was measured in [30– 33]. This model was used to evaluate the Setchenow constants for different gas/salt/temperature combinations in the range of 273–363 K.3865 + 0. This equation is derived from the integrated van’t Hoff equation and the logarithmic Setchenow salinity dependence. Ko for seawater as a function of salinity (S) and temperature (T. as it is know.

The effect of salinity is less pronounced at high temperatures.6 0. 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. H + F ↔ HF (7) Additionally insoluble calcium carbonate and magnesium hydroxide can be formed [41.3 0. These interactions can be deHCO– 3 3 scribed in terms of an ion association formalism and. the stoichiometric equilibrium constant of water in seasw can be expressed as: water Kw sw sw sw Kw = Kw / γH = [H + ]sw [OH − ]sw +γ OH − ( ) (8) (3) Culberson and Pytkowicz.12. Duan and Sun’s [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).1 Concentration in seawater (µmol/kg SW) 9. Al-Anezi.45 383. The Henry’s law coefficient of CO2 decreases with increasing temperature passes through a minimum at 170°C and increases again. temperature and salinity. . 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− . (6) Mg 2+ + OH − ↔ MgOH + 2− + − H + + SO4 ↔ HSO− 4 .4 . for pressures from 0 to 2000 bar.39]. Solubility of gases in the seawater is a function of their molecular weight.00934 Henry’s law coefficient (mol/(m3bar)) 29.4 206.00033 0. Table 2 [6.13. Their CO2 solubility model was based on the equation of state (EOS) of Duan et al.3 10. in terms of a specific interaction theory [6. more recently. N.7 6. The dissociation constant of water.4 10.15. Fig. 2− − Na + + CO3 ↔ NaCO3 . The Henry’s law coefficient also decreases with increasing salinity. − + Ca 2+ + HCO3 ↔ CaHCO3 . Mg2+. the dissociation of water obeys the equilibrium conditions and are important parts of carbonic acid equilibria [9.K.42].0 1. N2 and Ar. The dissociation of H2CO3 in water. But. this model relies on a complex virial EOS that needs to be solved iteratively.5 1.40]. Dickson and Riley. 1 was presented by Al-Rawajfeh [12] and it shows a schematic representation of the carbonate system in gas. Ca2+ and K+) and major anions (Cl–. [43–46] measured Table 2 Solubility data of the gases dissolved in seawater with S = 35 g/kg in equilibrium with the atmosphere at 25°C Gas CO2 N2 O2 Ar Partial pressure in atmosphere (bar) 0. liquid and solid phases. Hansson and Mehrbach et al.7808 0. where KW = [H + ][OH − ] (5) The carbonate system in seawater is characterised by the interaction of major cations (Na+. SO2– 4 2– and CO ). Hilal / Desalination 204 (2007) 385–402 389 However.15] shows the concentrations of the gases dissolved in seawater with a salinity of 35 g/kg in equilibrium with the atmosphere at 25°C and from this table we can see that CO2 is more soluble than O2. [37] and the theory of Pitzer [38.12.11 (mg/kg SW) 0.15.2095 0.18].

84226 − 3741.00574938S1. However.33291/T ) S 0. Basically all values of the solubilities and dissociation constants are temperature dependent. Millero [7]. Al-Anezi. measurable concentrations by the apparent solubility constant.390 K.5 sw ln K 2 = −0. since a combination of at least two of these parameters is needed to characterise the carbonate system. [52] investigated the parameters used to study the carbonate system such as pH. Millero [7] suggested two correlations for calculating the stoichiometric dissociation constants K1sw and K2sw and these correlations are based on the experimental data of [34.18867 − 2275.5 (11) .138681 9.9. Lueker et al.5 + 0. 1. For practical reasons the values of the dissociation constants are generally given as: pK = –10log K or K = 10–pK. the K values also depend on the solute concentrations. [47].44– 46.e.47].48–51] presented various correlations of the dissociation constants K1sw and K2sw of carbonic acid in seawater. Another correlation to calculate the equilibrium sw can be found in constant of water in seawater Kw another reference [44].468591ln T + ( −0.036/ T −1.437139ln (T ) + ( −0. in general. the equilibrium constant of water in seawater for temperatures up to 35°C and salinities up to 44 g/kg.00912840 S 1. Therefore. i.5 (10) + 0. In the non-ideal solutions of seawater and brackish water it is more practical to describe the relation between the real. Millero et al. Hilal / Desalination 204 (2007) 385–402 Fig.49]: ln K1sw = 2.1195308S −0.0726483S − 0. Schematic representation of the carbonate system. The thermodynamic solubility constant is: K o = γ a [H 2 CO3 ]/ PCO2 bilities and dissociation constants can sited elsewhere [6.11. the activity coefficients γ >1 (γ = 1 for an ideal solution. the concentrations have to be replaced by their activities that are smaller than the concentrations. with zero solute concentrations or zero ionic strength). N.128417 −24. fCO2 (fugacity) and TCO2. Full details of the correlations to calculate the solu- −1.41239 / T ) S 0. in the thermodynamic equation.17. 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. total alkalinity (TA).1288/ T (9) where. Many investigators as in [34.

2–6 show the solubility constants (= solubilities in M/L. Fouling. 2. N. scale deposits are formed mainly through thermal effects. (7)]. Hilal / Desalination 204 (2007) 385–402 391 where K 1sw and K 2sw are on the basis mol/kg seawater. The solubility constants (= solubilities in M/L. 3. In real-life situations.atm) and stoichiometric dissociation constants K1sw and K2sw for CO2 in freshwater. and multiple effect evaporation (MED) plants operate at temperatures lower than 70°C. T is in K and S is in g/kg. 5. at higher salinities similar to [30] [Eq. Consequently.K. 15. 88]. 25. Figs. pH increases and finally calcium carbonate precipitates. One of the major fouling phenomena encountered in the aqueous systems is scale formation due to precipitation of salts present in the water. . 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. Multi-stage flash (MSF) plants usually operate at temperatures as high as 120°C.atm) for CO2 in freshwater. the major risk of scaling is for minerals whose solubility decreases with increasing temperature. In fact. Al-Anezi. and 35‰ (= g of salt per kg of water) (upper graph) and as a function of salinity at 20°C (lower graph). seawater and brackish water as a function of temperature and salinities. All values are according to [7. the values for freshwater are similar to those in [89]. The mostly Fig. heating of the water has the consequence that carbon dioxide solubility decreases. alkaline scale formation and solubility product of calcium carbonate Fouling is the accumulation of undesired solid materials at the phase interfaces. Alkaline scale formation in seawater distillation begets from the decomposition hydrolysis of seawater bicarbonate ion as process temperature is increased [53]. seawater and brackish water as a function of temperature at salinities of 0.

88]. observed scales that occur in MSF distillers are found to be either CaCO3 or Mg(OH)2. and Mg2+ ions. 25. and 35‰. 3. 5. 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. The formation of the alkaline scales CaCO3 and Mg(OH)2 strongly depends on temperature. CaCO3 and CaSO4 are major fouling contributors [2. Hilal / Desalination 204 (2007) 385–402 Fig. The freshwater values are equal to those in [89]. Recent analysis of variation in coloration of water boxes came as a strong support to this hypothesis. The two are commonly referred to as alkaline scale. Al- . Meanwhile.54–61]. Lots of tions of HCO– 3 3 metals and anions exist naturally in the water. N. Ca2+. The values are according to [7. the presence of hydroxyl ions will be short lived primarily due to Mg(OH)2 precipitation. The abundance of magnesium ions and the extreme low solubility of magnesium hydroxide will then rapidly lead to its formation. A number of studies done by Al-Rawajfeh [3. the marine values are in good agreement with those reported in [46] as discussed in [48]. the release rate of CO2 as well as the concentra. CO2– . 12] Shams El Din and Mohammed [42]. The proposed steps support CaCO3 precipitation ahead of Mg(OH)2. 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. 15.392 K. However. Al-Anezi. 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. 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. among them.4. pH. and also suggested certain experiments that could verify the validity of his proposed reaction mechanism.

The freshwater values are equal to those in [89].58. Rawajfeh et al. which can take into account the fluid flow effect using a specific approach based on a scheme of serially connected homogeneous reactors. calcium sulfate. and calcium sulphate. Azaroual et al. [62] to analyze scale formation in seawater distillers which is mainly caused by crystallization of the inversely soluble salts calcium carbonate. A simple and easy programmed code is pro- posed by Al-Shammiri et al.K. barium sulfate. N. CO2– . Hilal / Desalination 204 (2007) 385–402 393 Fig. it plays an im3 portant role in alkaline scale formation. H+ and OH– concentraand the HCO– 3 3 tions in the brine on its flow path through multipleeffect distillers. calcium fluoride and strontium sulfate scaling.18. and 35‰. 25. [63] for estimating the scaling potential for different scaling species that expected to be precipitated in an RO system. [64] presented a thermokinetic geochemical calculation program (SCALE2000) based on Pitzer’s ion interaction model. 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. Thus.62] is very useful to calculate the CO2 release rates .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. Al-Rawajfeh [3] proved that the model developed by Al-Rawajfeh [3. magnesium hydroxide. Al-Anezi. the marine values are in good agreement with those reported in [46] as reported in [48]. According to the authors [64. 4. . 15. CO2. as calcium carbonate. CO2 release and alkaline scale formation in seawater distillers are closely related to the carbonate system in the brine. 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.12. The values are according to [88]. 5.

88. CT. The values are calculated at temperatures of 5 and 25°C and for salinities of 0 and 35‰ as a function of the pH. the carbon distributions are shown for an (unrealistic) wider range of pH values. Values for the first and second dissociation constants of dissolved carbonic acid as a function of the salinity. 5. Seawater has pH values around 8. Distribution of the carbonic acid fractions as a percentage of the total carbon content. However.88]. Fig. Values for the first and second dissociation constants of dissolved carbonic acid as a function of the salinity [7. Al-Anezi. Hilal / Desalination 204 (2007) 385–402 Fig.394 K. to illustrate the dependence of the carbon distribution on salinity [7. 6.90].2. . The values are valid for a water temperature of 20°C. N.

S = 60 g/kg and p = 10 bar. [64]. Thus. Ksp and salinity but decrease with temperature. At T = 30°C. ai and bi as ion specific parameters Approximation Debye–Hückel Extended Debye–Hückel Equation Applicability 2 i log γ i = − Az I I 1 + Bai I I 1 + Bai I + bi I I < 0. Al-Anezi. the pressure dependence of the equilibrium constants can be neglected. Ksw and Kw differ from the values at 1 bar by Ksw 1 2 sw differs 1%.19.1 mol/kg log γ i = − Azi2 log γ i = − Azi2 WATEQ–Debye–Hückel I < 1 mol/kg Davies log γ i = − Azi2 ⎜ ⎛ I ⎝1+ I − 0. Hilal / Desalination 204 (2007) 385–402 395 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 / γ Ca = [Ca 2+ ]sw ⋅ [CO3 ] 2+ ⋅ γ CO 2− 3 ( ) (13) where Ksp is the thermodynamic solubility product are the concentration and the and [i]sw and γsw i activity coefficients of the component i. respectively. B as temperaturedependent parameter.3%. Much of their behaviour can be correlated in terms of the ionic strength defined by: I=1 2∑ zi2 mi (14) In general. respectively.68–72]. respectively [8].1 mol/kg useful for mixed electrolytes Güntelberg I log γ = − Az 2 i i 1+ I .8. [12] has summarised the theoretical expressions for the activity coefficients in Table 3 [6. 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.25.5 mol/kg I < 0. A as the Debye–Hückel parameter which depends on the dielectric constant of the solvent and on the temperature. 0. for small and moderate pressures. for water at 25°C A = 0. sw of calcite and aragonite. N.005 mol/kg I < 0. Zuddas and Mucci [67] for a salinity between 5 and 45 g/kg and a temperature between 5 and 40°C at 1 atm sw values increase with pressure total pressure. Sheikholeslami and Ong [61]. Ksp from the values at 1 bar by 0.3% and 0. Azaroual et al. The activity coefficients in reality are complex functions of the composition of the aqueous solution.2 I ⎟ ⎞ ⎠ I < 0. In electrolyte solutions. can Ksp be calculated from correlations reported by Dickson and Millero [48]. Al-Rawajfeh. the values of sw . the activity coefficients are influenced mainly by electrical interactions.3%.K.509 kg1/2 mol–1/2. 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. Mucci [66].

23 0. such ]. 3.4819 + 0. following from the conservation of electroneutrality in solutions where the metal ion concentrations (Na.51. The alkalinity is a practical quantity. In this version of Debye–Hückel equation a simple term.69.65. It is only accurate up to ionic strengths of a few tenths molal in most solutions.17 1.9.5 mol/kg.3 value. 2.52. This term improves the empirical fit to higher ionic strength but it has no theoretical justification [12. Al-Anezi. three pH scales have been proposed (seawater scale. Total carbon dioxide content. (15) is used in many of the chemical equilibrium systems because of its simplicity.203 1.69 0. TA. Davies’ Eq.23 and for trivalent ions γi = 0. evaporation or dilution. Total alkalinity. Concentration of dissolved CO2 [CO2]. Hilal / Desalination 204 (2007) 385–402 Table 4 Activity coefficients for some species in seawater (S = 35 g/kg) at 25°C Species Activity coefficient in seawater (I = 0. Mg) and pH are constant. was added at the end of the equation.669 0. The Davies equation is normally only used for temperatures close to 25°C. Concentration of carbonate ions [CO2– 3 4. linear in I. The activity coefficients for seawater (I = 0. pH value or concentration of H+ ions [H+] or concentration of OH– ions [OH–].75].e. [17] presented the normalized values NTA and NTC which are defined as follows: . has the advantage that it needs no adjustable ion size parameter.396 K.649 0. so. [B(OH)– 4 in seawater. 4. Concentration of bicarbonate ions [HCO– 3 ]. Alkalinity and total carbon dioxide are both conservative properties (i. Carbonate system and chemical kinetics The carbonate system in seawater have been described in [6.2 with 0. TC: − 2− TC = [HCO3 ] + [CO3 ] + [H 2 CO3 ] (16) 6. which is valid for I < 0. and free proton scale [79–81]). to remove these variations Millero et al.167 (15a) where T is the temperature in °C.7. ]. Stumm and Morgan [40] related the total alkalinity TA to chlorinity. and it is known that TA and TC vary as a result of any changes in salinity due to mixing. for divalent ions γi = 0. For seawater samples.0011T Davies equation 0.72 mol/kg) are for monovalent ions γi = 0. total proton scale.69 0.04 (Table 4). salinity is conservative).69 0.2I ⎤⎦⎥ (15) It should be noted that many other workers have replaced the value of 0. Loewenthal and Marais [11] concluded that these values are realistic even though seawater ionic strength is outside the valid range of this equation.23 0.72 mol/kg) Loewenthal and Marais Na Ca2+ HCO– 3 Cl– CO2– 3 CO2 + describe the concentration dependence of activity coefficients: log γ i = − Aγ ⋅ zi2 ⎡ ⎢ ⎣ ( I / (1 + I )) − 0. as humic acids in freshwater or borate. Cl. N.248 0.74. 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. With zi as the charge of the ion Helgeson and Kirkham [73] presented an interpolation formula to calculate the Debye–Hückel constant A: A = 0.693 0.72. Ca. 5.76–78] by the following six quantities: 1.58.

In our study of the solubility of CO2 in seawater we will be using these reaction mechanisms to determine the reaction rates. NTC.82–84] have described the reaction mechanisms and reaction rates of the hydration and dehydration of CO2 in aqueous bicarbonate–carbonate solutions. 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. They evaluated the CO2 solubilities by the Ostwald coefficient. gas burettes. and 35°C. 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.8. and they concluded that this technique had an applicability wider than the deter- mination of solubilities and simple reaction rates. 5. Many authors [6. precisely expressed as the fugacity fCO is determined from dissolved inorganic carbon 2 DIC and total alkalinity TA. careful consideration should be taken into account for the effect of temperature. If a study of CO2 solubility is to be carried out for conditions similar to those in MSF plants. The partial pressure of carbon dioxide in the ocean’s surface waters. 25. Hilal / Desalination 204 (2007) 385–402 397 NTA = TA X ( 35/ S ) (18) and NTC = TC X ( 35 / S ) (19) with NTA. and pH. and many workers have suggested certain reaction mechanisms trying to better understand the reaction kinetics that takes place in these conditions. TA and TC in mol/kg and S in g/kg. Vapor–liquid 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. the solubility of a gas in water decreases as the water warms. A bubble column reactor has been designed by Shorter et al. The device. 4. They found that CO2 solubility is slightly lower in a 1 wt % NaCl solution than in pure water due to the saltingout effect.K. Generally. 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. manometer and a stirrer of magnet coated with glass in it. has a unique utility in studying interactions at the gas–liquid interface. N. L and concluded that the empirical Setschenow equation was not applicable to some systems. Yasunishi and Yoshida [29] and Tokunaga [85] used an apparatus that was comprised of an absorption chamber. The data of those systems were correlated by a two-parameter equation within a deviation of 2%. and it is known . They have presented parallel reaction mechanisms and presented many correlations to calculate the reaction rate constant and reaction time. salinity. [86] to study the uptake of gas in liquid. for example. A PVT apparatus was designed by Nighswander et al. reaction time and the rate constants since it is known that the reaction rate depends on the temperature.33. 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. the pressure and the ionic strength. [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 200°C and pressure up to 10 MPa. Al-Anezi. pressure.

Al-Anezi. Desalination: present and future. Semiat. atm 2 S — Salinity of the seawater.M. mol/kg First dissociation or acidity constants Second dissociation or acidity constants Thermodynamic equilibrium constant of water Stoichiometric equilibrium constant of water in seawater. Acknowledgements We would like to thank The Public Authority of Applied Education in Kuwait (PAAET) for funding this work. pH rise caused by the carbon dioxide loss involves calcium carbonate precipitation. Reddy. Oxford. Symbols A aq ci Cl g h — — — — — — Debye–Hückel constant Dissolved phase Concentration of the ion i.398 K. In MSF desalination plants fouling occurs as a result of CO2 release and alkaline scale formation in seawater distillers. Glade and K. m3/kmol Ionic strength. Acid–Base Chemistry of Aquatic Systems: An Introduction to the Chemistry of Acid–Base Equilibria with Emphasis on the Carbon Dioxide System in Natural Waters. Glade and J. [5] H.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. Genthner. g/kg Gaseous phase Summation of ion specific parameters of the positive ions (h+). 25(1) (2000) 54–65. m3/kmol Gas-specific part of the Setchenow constant. In: Encyclopedia of Desalination and Water Resources. 182 (2005) 203–213. AlGobaisi. 156 (2003) 1–20. M. 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 γsw CO γisw 2 KG. Due to high temperatures encountered in the desalination plants. negative ions (h–) and the gas specific parameter (hG) Ion-specific parameter.o — Activity coefficient of carbon dioxide — Activity coefficient of the component i that is free or involved in ion pairing References [1] R. [3] A. mol L–1 atm–1 or moles kg–1 atm–1 — Gas solubility in water. Al-Sofi. Hunter. °C or K TA — Total alkalinity. EOLSS Publishers Co.. Al-Rawajfeh. PCO 2 PCO . The problem of noncondensable gas releases in evaporators. Fouling phenomena in multi-stage flash (MSF) distillers. [4] M. [6] K. Water Intern. Review of MEDRC R&D projects. Desalination. [2] K. Desalination. Hilal / Desalination 204 (2007) 385–402 that high temperature conditions are usually encountered in desalination plants. N.K. kmol/m3 Chlorinity. H..A. Ulrich. g/kg T — System temperature. hi hG HG I K1 K2 KW Kwsw — — — — — — — — Ko. Therefore.. m3/kmol Gas-specific parameter. 1998.A.K. mol/kg seawater Gas solubility coefficient in salt solution. KG — . D. Desalination.E. Scaling in multiple-effect distillers: the role of CO2 release. moles kg–1 atm–1 KG. Abu Arabi and K. Cited 10 May 2005.K. 2000. Ltd.. ed. 126 (1999) 61– 76. there is a need for in-depth knowledge of solubility of CO2 in seawater. Quteishat.

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