Chemical Engineering Science 55 (2000) 2663}2671

Vapor}liquid}solid equilibria of sulfur dioxide in aqueous electrolyte solutions

Selva Pereda, Kaj Thomsen, Peter Rasmussen*
IVC-SEP, Department of Chemical Engineering, Technical University of Denmark, Building 229, DK-2800 Kongens Lyngby, Denmark Received 28 July 1999; received in revised form 22 October 1999

Abstract The Extended UNIQUAC model for electrolyte systems, combined with the Soave}Redlich}Kwong equation of state is used to describe the complex vapor}liquid}solid equilibria of sulfur dioxide in electrolyte solutions. Model parameters based on 1500 experimental data points are presented. The parameters are applicable in the temperature range 0}1103C, concentrations up to saturation and pressures up to 30 bar. This validity range corresponds to the experimental data used for the evaluation of parameters. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: VLSE; Solubility; Sulfur dioxide; Aqueous electrolytes; Extended UNIQUAC

1. Introduction There is considerable interest in the solubility of sulfur dioxide because of its importance in industrial applications and in pollution control. Sulfur dioxide as pollutant may be removed from air or from other gases like #ue gas in power plants, by absorption in aqueous electrolyte solutions. The study of the equilibria involving sulfur dioxide is also useful for the paper industry. A thermodynamic model is an indispensable tool in order to design, optimize and simulate processes with this system. In this work the Extended UNIQUAC model for activity coe$cients, combined with the SRK equation of state for the fugacities in the vapor phase, is used to describe the complex equilibria with chemical reactions for sulfur dioxide in electrolyte solutions. A description of the Extended UNIQUAC model was given by Thomsen and Rasmussen (1999), along with parameters for aqueous systems involving CO , NH ,   H>, Na>, K>, NH>, Cl\, SO\, OH\, NO\, HCO\,     CO\ and NH COO\. The model equations are present  ed by Thomsen, Rasmussen and Gani (1996). The only parameters needed in the Extended UNIQUAC model are the binary interaction parameters together with volume and surface area parameters for the

di!erent species. For the use of the SRK equation of state in this work, only the critical properties and the acentric factors for SO and H O are needed, and thus no SRK   interaction parameter. The electrolyte solutions considered in this paper may contain four di!erent cations (H>, Na>, K>, NH>) and  three di!erent anions (Cl\, SO\, OH\) besides the  species produced when sulfur dioxide is dissolved in water (SO (aq), HSO\, SO\, S O\).      Nine di!erent salts can be formed in SO -electrolyte  solutions with Na>, K> and NH> at the temperatures  considered in this work. The precipitation of these salts can be properly described by the model. The vapor pressures and the thermal properties of the considered systems are also well described.

2. The SO2 }electrolyte solution system By absorption of sulfur dioxide in aqueous electrolyte solutions, several reactions take place. The following equilibria are considered in this work, Vapor}liquid equilibria: SO (g) 0 SO (aq).   Speciation equilibria: SO (aq)#H O(l) 0 H>#HSO\,   

* Corresponding author. Tel.: 00-45-4525-2877; fax: 00-45-4588-2258. E-mail address: pr@kt.dtu.dk (P. Rasmussen).

0009-2509/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved. PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 5 3 5 - 7

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Nomenclature CNP C N D G D H FPD P m apparent molal relative heat capacity standard state heat capacity standard state Gibbs energy of formation standard state enthalpy of formation freezing point depression apparent molal relative enthalpy molality

P q r wt%

pressure surface area parameter volume parameter temperature weight percent

Greek letter activity coe$cient

HSO\ 0 H>#SO\,   2HSO\ 0 S O\#H O.    Liquid}solid equilibria: 2NH>#SO\ 0 (NH ) SO ,     2NH>#SO\#H O 0 (NH ) SO ) H O,       2Na>#SO\ 0 Na SO ,    2Na>#SO\#7H O 0 Na SO ) 7H O,      2K>#SO\ 0 K SO ,    2NH>#S O\ 0 (NH ) S O ,       2Na>#S O\ 0 Na S O ,      2Na>#S O\#7H O 0 Na S O ) 7H O,        2K>#S O\ 0 K S O .      3. Parameter estimation The parameter estimation was based on experimental data in the temperature range from 0 to 1103C, pressures up to 30 bar and the concentration range from in"nite dilution to saturation. The parameter estimation was carried out as described by Thomsen et al. (1996). The database comprised 700 experimental values for vapor}liquid equilibrium and more than 500 experimental solid}liquid equilibrium data. Also thermal properties, activity coe$cients and osmotic coe$cients calculated from freezing point depression data were used, giving a total of 1500 experimental points, that were included in the parameter estimation. A number of additional experimental data were excluded from the parameter estimation for reasons discussed below. A list of sources containing SLE-data that was used in the parameter estimation is presented in Table 1. Table 2 lists the sources of freezing point depression, activity coe$cients and thermal property data. Only a few of the values for the standard state Gibbs energy of formation and the standard state heat capacity

Table 1 References: solid liquid equilibria data System NH Cl}(NH ) SO }(NH ) SO      Na SO }(NH ) SO }(NH ) SO       NaCl}Na SO }Na SO     NaCl}(NH ) SO }Na SO }NH Cl      Na SO }Na SO     NH HSO }(NH ) SO     (NH ) SO }NH HSO     (NH ) SO }(NH ) SO     (NH ) SO   (NH ) SO }(NH ) SO }NH HSO       Na SO }Na S O      Na SO   NaCl}Na SO   Na SO   Na S O    K SO   K S O    Na SO   Na SO }NaOH   KHSO  Na SO }NaHSO    NH }SO   (NH ) SO }Na SO     Na SO }(NH ) SO }NaCl}NH Cl      NaHSO }NH HSO }NaCl}NH Cl     (NH ) SO   (NH ) SO }(NH ) SO     NH }SO   NH }SO   (NH ) SO }(NH ) SO     (NH ) SO }NH HSO     Source Labash and Lusby (1955a) Labash and Lusby (1955a) Labash and Lusby (1955a) Labash and Lusby (1955b) Rivett and Lewis (1923) Vasilenko (1948) Vasilenko (1949) Vasilenko (1950) Vasilenko (1950) Vasilenko (1953) Arii (1932) Kobe and Hellwig (1955) Kobe and Hellwig (1955) Foerster et al. (1924) Foerster et al. (1924) Foerster et al. (1924) Foerster et al. (1924) Hartley and Barret (1909) Llewellyn and Currie (1925) Platt and Hudson (1926) Buzek et al. (1995) Hill (1948) Zilberman and Ivanov (1941) Zilberman and Ivanov (1941) Zilberman and Ivanov (1941) Ishikawa and Murooka (1933a) Ishikawa and Murooka (1933b) Ishikawa and Hagisawa (1933) Terres and Hahn (1927) Terres and Heinsen (1927) Terres and Heinsen (1927)

for the salts, G and C , necessary to describe the D N system, were found in the literature. G and C for D N Na SO were found in the NIST tables (NIST, 1990).   For the rest of the salts these properties were "tted to experimental data. For several salts, values of the standard state enthalpy of formation, H, were found in D the NIST tables, except the values for Na SO ) 7H O,   

S. Pereda et al. / Chemical Engineering Science 55 (2000) 2663}2671

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Na S O ) 7H O, (NH ) SO ) H O and (NH ) S O .           These values were thus estimated from the experimental data. All the values are listed in Table 3 together with the thermodynamic properties for gaseous SO . G and  D H for aqueous SO and for the ions were found in the D  NIST tables. A three parameters correlation was used for the temperature dependence of the standard state heat capacity of the ions (Thomsen et al., 1996; Thomsen, 1997).

4. Results and discussion The extended UNIQUAC binary interaction energy parameters for the species SO (aq), HSO\, SO\ and    S O\, that were estimated in this work are presented in   Table 4. In Table 5, the r and q parameters are listed along with the standard state properties of each species. The results of the VLE-data correlation performed in this work are shown in Figs. 1}3 and in Tables 6}8. Experimental data are plotted along with the calculated curves. Fig. 1 presents the total pressure of the system

Table 2 References: freezing point depression (FPD), activity coe$cients ( ) and thermal properties (C , ) NP P Property FPD FPD FPD FPD FPD System Na S O    K S O    Na SO   K SO   Na SO   Na SO   Na SO   SO  NaHSO  KHSO  Na SO   Source Foerster et al. (1924) Foerster et al. (1924) Foerster et al. (1924) Foerster et al. (1924) Hartley and Barret (1909) Morgan (1961) Lantzke, Covington and Robinson (1972) Barbero et al. (1983) Barbero et al. (1983) Barbero et al. (1983) Vanderzee and Noll (1983)

C NP C NP C NP P

SO }water at six di!erent temperatures between 0 and  603C. Fig. 2 shows the partial pressure of SO for the  system SO }water, at constant concentration of sulfur  dioxide and varying temperatures. In Table 6, the experimental data for the system SO }water used for the para meter estimation is presented. The concentration, temperature and pressure range of each data set, together with the number of data points used are listed. Some of the papers may contain more experimental data, outside the range covered in this work. Also the average relative deviation in percent between the calculated and the experimental values of the pressure for each data set is shown. For the VLE-data at low pressure, the mean absolute deviation of the partial pressure is presented. For these data the relative deviations are high although the absolute deviations are within the limit of the precision of the experimental data. It cannot be expected that experimental VLE-data can be reproduced with a relative deviation less than 5}10%, the typical range of error in the measurement of the vapor pressure, Thomsen and Rasmussen (1999). The data set of Freese (1920) deviates more than 10% from the calculated values. These data also deviate strongly from other comparable data in the SO }H O system.   These data were therefore not used in the parameter estimation. Fig. 3 and Table 7 show the results for the system SO }NH }water. As shown in Fig. 3 the addition of SO    at low concentration causes the total pressure of the system to decrease. This is due to the chemical reactions that take place in the solution resulting in the decrease of the pressure of both gases. When almost all the ammonia contained in the liquid phase has been converted to its ionic form an increase of the pressure is observed, Rumpf, Weyrich and Maurer (1993). Table 8 shows the experimental data and the results for the ternary system sulfur dioxide}electrolyte}water. Almost all the data sets show good agreement between experimental and calculated values. Only the measurements from Fox (1902) for the systems with NaCl and

Table 3 Standard thermodynamic properties for the salts and gaseous SO  Species SO (g)  (NH ) S O    (NH ) SO   (NH ) SO ) H O    K S O    K SO   Na S O    Na S O ) 7H O     Na SO   Na SO ) 7H O    ! D G3 (kJ mol\) ! D H3 (kJ mol\) C (J mol\ K\) N 39.870 524.80 258.017 289.543 436.796 435.506 121.767 643.69 120.25 194.019

300.194 959.586 637.531 880.737 1377.043 1046.70 1333.569 2991.55 1012.50 2676.10

296.830 1298.08 885.30 1199.464 1533.90 1125.50 1478.20 3555.75 1100.80 3162.47

Value from the NIST table. NIST (1990).

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Na SO have deviations higher than the acceptable. The   experimental data were presented as absorption coe$cients and the conversion to the molality scale may increase the uncertainty in the experimental data. Also considering that the work is from 1902 it was decided not to use these two sets of data in the parameter estimation. The ternary system SO }HCl}water was studied by  Krissmann, Siddiqi and Lucas (1997) at di!erent concentrations of HCl. They found that at higher concentrations of HCl than 0.5 m the complex SO Cl\ is formed. Since  this species is not included in the chemical system described in this work, the isotherms at concentrations of HCl higher than 0.1 m were not included. In Fig. 4, the apparent molal relative heat capacities at 253C for SO , KHSO and NaHSO measured by Bar   bero, Hepler, McCurdy and Tremaine (1983) are shown together with the calculated values. The e!ect of chemical relaxation (speciation) is included in the calculated and the experimental values. Fig. 5 shows the very good agreement between calculated and experimental values of the apparent molal relative enthalpy of Na SO at 253C.   The calculations of liquid}solid equilibria by the Extended UNIQUAC model is shown in Figs. 6}8. Fig. 6 shows the calculated and experimental values for the single salt solubility for all the salts considered in this work. It can be seen that the model represents the solubility of the nine salts very well. Fig. 7 shows the solubility in the NaCl}Na SO }H O    system at 25, 40, 60 and 1003C. At the three higher temperatures the solid phases present are NaCl and Na SO . At 253C the di!erence in the shape of the   solubility curve is due to the appearance of a third salt Na SO ) 7H O. The model predicts for this system that    between 18 and 333C both salts, Na SO and   Na SO ) 7H O, can precipitate besides NaCl. This sys   tem was studied by Kobe and Hellwig (1955) and Labash and Lusby (1955a) at 25 and 203C, respectively. None of these researchers found anhydrous Na SO at these tem  peratures, but they also could not locate a univariant point where NaCl and Na SO ) 7H O are in equilib   rium with the same solution. Kobe and Hellwig (1955) measured the concentrations of the univariant points for all the temperatures they studied, except at 253C. At this temperature, they calculated the univariant point by extrapolation of the NaCl and the Na SO ) 7H O equilib   rium curves. Labash and Lusby (1955a) found that the "eld of NaCl ends at di!erent concentrations from where the "eld of Na SO ) 7H O ends, and they refer to the    solid phase between these two points as undetermined. Labash and Lusby (1955a) also measured the solubility in the Na SO }(NH ) SO }water system at 203C. In     this system they had the same problem, of an undetermined salt. The Extended UNIQUAC model again predicts the precipitation of anhydrous Na SO from 173C,   where the invariant point is located. Fig. 8 shows the experimental data together with the results calculated

854.229

S O\  

1150.65 929.414

SO\ 

HSO\ 

68.596 484.066 2500 628.602

SO

2500 2500 1303.68 2500

OH\

1034.35 1117.08 1170.09 908.01

SO\ 

1560.47 1638.48 2376.40 2500

Cl\

16.347 13.709 9.5139 0 This value was assigned to the parameter due to model considerations Thomsen (1997). This value was assigned to the parameter due to chemical considerations. Thomsen (1997). The value was not estimated but assigned a "xed value due to insu$cient data. 3.0583 !0.3236 !1.4393 !0.3242 0 0 0 0 !0.5156 9.2903 10.468 1.8535 1.6899 !2.2595 !3.3140 0.56392 0 0 !2.0540 0 1.9714 1.2505 !0.7345 !0.2173

Table 4 UNIQUAC interaction energy parameters (u "u #uR (!298.15)) in Kelvin GH GH GH

K>

Na>

H O 

u "u HG GH SO (aq)  HSO\  SO\  S O\   uR "uR GH HG SO (aq)  HSO\  SO\  S O\  

78.116 391.107 405.175 567.792

10 10 10 10

H>

50.877 963.88 989.632 1099.49

78.021 1655.81 1324.43 1615.40

2500 2500 2169.36 2500

NH 

!117.72 328.88 415.88 636.80

NH> 

12.579 4.5110 7.0196 11.744

0 0 !2.8621 0

3.6018 2.8049 0 3.5185

0.56528 !3.5272 0.16987

867.736 901.178 670.051

!5.6895 1.4506

0.27307

S. Pereda et al. / Chemical Engineering Science 55 (2000) 2663}2671 Table 5 UNIQUAC r and q parameters, a, b and c parameters for C (J mol\ K\), G3 and H3 N D D r SO (aq)  HSO\  SO\  S O\   2.5410 11.154 10.603 9.0304 q 3.6745 9.7851 9.7640 11.848 a 195.00 !0.65657 1050.29 !0.92424 b 0 0.33697 !3.01755 0.286059 c 0 !9853.00 !26024.9 !10800.1 ! D G3 (kJ mol\) ! D

2667

H3 (kJ mol\)

300.67 527.73 486.50 808.61

322.98 626.22 635.50 973.60

Parameters for the temperature dependence for the C of the ions C"a#b(K)#c/((K)!200). N N Value from NIST table. NIST (1990). Heat capacities for this species is considered independent from the temperature.

Fig. 1. Total pressure for the binary system SO }water. Sources:  Rumpf and Maurer (1992), Johnstone, Read and Blankmeyer (1938), Campbell and Maass (1930), Hudson (1925), Maass and Maass (1928), Morgan and Maass (1931), Johnstone and Leppla (1934), Hunger (1990) and Parkinson (1956).

Fig. 3. Total pressure of the ternary system SO }NH }water.  

Fig. 2. Partial pressure of SO in the binary system SO }water at four   di!erent concentrations.

by the model in the quaternary (NH ) SO }   (NH ) S O }(NH ) SO system.      Terres and Heinsen (1927) studied the system (NH ) SO }(NH ) SO }H O over a wide range of     

temperatures. Later Ishikawa and Murooka (1933a) and Vasilenko (1950) made a careful study of the same system. The results of these authors are in good agreement and they both claimed that the results of Terres and Heinsen (1927) are not correct. The data of Terres and Heinsen were therefore excluded from the parameter estimation. Also the data published by Terres and Hahn (1927) for the NH }SO }water system were not used for the para  meter estimation. This system was later studied by Ishikawa and Hagisawa (1933) and by Hill (1948), and again a signi"cant discrepancy was found concerning the data of Terres and Hahn. For concentrations under 20 wt% of SO in this system the Extended UNIQUAC  model is in disagreement with the data presented by Hill and Ishikawa and Hagisawa. Foerster, Brosche and Schulz (1924) and Platt and Hudson (1926) studied the solubility of KHSO in water.  Signi"cant discrepancies were found between these two sets of measurements, the solubilities measured by Platt and Hudson are more than 10% lower than those measured by Foerster. Since Platt and Hudson state in their work that they only measured the `approximate solubilitya of KHSO , it was decided not to include the data of  Platt and Hudson in the parameter estimation.

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Table 6 Results for the binary sulfur dioxide}water system m SO  1.2}2.9 0.002}0.03 0.01}2.58 0.08}1.16 0.005}0.12 0.70}4.68 0.90}1.36 0.09}0.69 0.15}1.15 0.87}4.13 0.14}2.42 0.22}5.55 (K) 279}303 298}323 273}298 296}379 283}305 283}300 298}308 303}353 298}383 273}313 283}363 293}363 P (bar) 1.0 0.03}0.13 0.008}1.11 0.12}2.15 0.01}0.08 0.32}3.4 1.0 0.09}1.19 0.14}4.5 1.0 1.02}1.28 0.35}16.4 Source Douabul and Riley (1979) Johnstone and Leppla (1934) Morgan and Maass (1931) Beuschlein and Simenson (1940) Parkinson (1956) Maass and Maass (1928) Fox (1902) Rabe and Harris (1963) Campbell and Maass (1930) Freese (1920) Hudson (1925) Rumpf and Maurer (1992) N 6 16 38 51 40 29 2 18 55 17 20 48 P(total) P(SO )  P(SO )  P(SO )  P(SO )  P(total) P(total) P(SO )  P(total) P(total) P(total) P(total) Dev% 5.1 0.0005(bar) 6.96 6.48 0.0017(bar) 2.90 3.13 3.15 5.9 16.25 1.44 3.38

Mean absolute deviation in the partial pressure. Experimental data at very low partial pressure.

Table 7 Results for the vapor pressure of the ternary sulfur dioxide}ammonia}water system m SO  0}10.52 2.90}11.29 2.90}11.29 2.90}11.29 m NH  3.19}6.08 3.22}12.41 3.22}12.41 3.22}12.41 (K) 313}373 308}363 308}363 308}363 P (bar) 0.18}21.89 0.04}0.62 0.04}0.62 0.04}0.62 Source Rumpf et al. (1993) Johnstone (1935) Johnstone (1935) Johnstone (1935) P P(total) P(total) P(NH )  P(SO )  N 87 13 30 30 Dev% 3.89 5.97 0.0088(bar) 0.0227(bar)

Mean absolute deviation in the partial pressure. Experimental data at very low partial pressure.

Table 8 Results for the ternary sulfur dioxide}electrolyte}water system Salt NH Cl  NaOH NaCl Na SO   Na SO   Na SO   Na SO   KCl KCl K SO   HCl (NH ) SO   (NH ) SO   mol kg\ 0.51}3.39 2.21}4.32 0.50}3.19 0.00}3.12 0.50}3.22 0.00}1.00 0.50}1.00 0.00}5.11 0.50}3.32 0.51}1.05 0.001}0.1 0.52}3.80 2.00}4.00 (K) 298 308}363 298 293}323 298}308 298 312}363 283}363 298}308 298 298 298}308 333}363 P (bar) 1.0 0.05}0.7 1.0 1.0 1.0 0.03}0.04 0.1}17.8 1.0}1.3 1.0 1.0 0.03 1.0 0.5}19.1 Source Fox (1902) Johnstone et al. (1938) Fox (1902) Hudson (1925) Fox (1902) Hunger, Lapicque and Storck (1990) Rumpf and Maurer (1993) Hudson (1925) Fox (1902) Fox (1902) Krissmann et al. (1997) Fox (1902) Rumpf and Maurer (1993) N 6 41 6 26 12 8 38 44 12 2 19 12 32 P(total) P(SO )  P(total) P(total) P(total) P(SO )  P(total) P(total) P(total) P(total) P(SO )  P(total) P(total) Dev% 1.71 0.002(bar) 19.89 4.36 10.61 0.0032(bar) 6.99 1.77 2.38 2.09 0.0002(bar) 4.58 8.54

Mean absolute deviation in the partial pressure. Experimental data at very low partial pressure.

Several authors studied the solubility of Na SO in   water. The data of Hartley and Barret (1909) present signi"cant di!erences from the rest of the authors in the "eld where anhydrous Na SO precipitate. The data   were therefore not included. Buzek, Jaschik and Jaschik (1995) measured the salt solubility in the Na SO }   NaHSO }H O system. Their solubilities of Na SO in     water are low compared with the results of other authors,

as also shown by Buzek et al. The data of Buzek et al. (1995) were not included in the parameter estimation because they seem to be in disagreement with the rest of the published data. Rivett and Lewis (1923) studied the Na SO }   Na SO }water system. They found that solid solutions   appear in this system. We did not attempt to model the solid solution. The model was used later to simulate this

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Fig. 4. Apparent molal relative heat capacity at 253C.

Fig. 6. Single salt solubility in water. Foerster (1924), Arii (1932), Ishikawa and Murooka (1933a), Vasilenko (1948), Vasilenko (1949), Vasilenko (1950), Kobe and Hellwig (1955) and Labash and Lusby (1955a).

Fig. 5. Apparent molal relative enthalpy of Na SO at 253C.   Fig. 7. Salt solubility in the Na SO }NaCl}water system at 25, 40, 60   and 1003C.

system at the temperature investigated by Rivett and Lewis, and the model predicts with good accuracy the solubility of Na SO in this system.   Labash and Lusby (1955b) studied the quaternary NaCl}NH Cl}Na SO }(NH ) SO system at 20 and      603C and Zilberman and Ivanov (1941) studied it at 60 and 853C. None of these data sets were used in the parameter estimation. The data of Zilberman and Ivanov were not included since these measurements in general a!ect the results obtained with the rest of the data in a negative way. The data of Labash and Lusby were not included since the authors did not identify the solid phase. The Extended UNIQUAC model was used to predict the data of Labash and Lusby giving good results.

5. Conclusion The complex phase behavior together with the thermal properties of the system SO in aqueous electrolyte solu tions has been treated. The extended UNIQUAC model for electrolytes combined with the Soave Redlich Kwong * cubic equation of state, has been shown to be an adequate thermodynamic model for this system. The model only requires binary interaction parameters and UNIQUAC volume and surface area parameters for each species. The standard thermodynamic properties for the species present in the system are also required. It should be noted that for the proper use of the model, the

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S. Pereda et al. / Chemical Engineering Science 55 (2000) 2663}2671 Hill, L. M. (1948). The system ammonia}sulfur dioxide}water at 253C. Journal of Chemical Society, 76}78. Hudson, J. (1925). The solubility of sulfur dioxide in water and in aqueous solutions of potassium chloride and sodium sulfate. Journal of Chemical Society, 127, 1332}1347. Hunger, T., Lapicque, F., & Storck, A. (1990). Thermodynamic equilibrium of diluted SO absorption into Na SO or H SO electrolyte      solutions. Journal of Chemical Engineering Data, 35, 453}463. Ishikawa, F. & Hagisawa, H. (1933). Studies on the ammonium sul"te part III. Equilibrium in the system SO }NH }H O. Science Report    of the Tohoku Imperial University, 22, 235}243 (English). Original: L (1931) Bulletin of the Institute of Physics and Chemistry Research, 10, 166}172 (Japanese). Ishikawa, F. & Murooka, T. (1933a). Studies on the ammonium sul"te part I. The solubility and the transition point of ammonium sul"te. Science Report of the Tohoku Imperial University, 22, 201}219 L (English). Original: (1928) Bulletin of the Institute of Physics and Chemistry Research, 7, 1160}1176 (Japanese). Ishikawa, F. & Murooka, T. (1933b). Studies on the ammonium sul"te part II. Equilibrium in the system ammonium sul"te}ammonium sulfate}water. Science Report of the Tohoku Imperial University, 22, L 220}234 (English). Original: (1929) Bulletin of the Institute of Physics and Chemistry Research, 8, 75}88 (Japanese). Johnstone, H. (1935). Recovery of sulfur dioxide from waste gases. Industrial and Engineering Chemistry, 27, 587}593. Johnstone, H., & Leppla, P. (1934). The solubility of sulfur dioxide at low partial pressures. The ionization constant and heat of ionization of sulfurous acid. Journal of American Chemistry Society, 56, 2233}2238. Johnstone, H., Read, H., & Blankmeyer, H. (1938). Recovery of sulfur dioxide from waste gases. Industrial and Engineering Chemistry, 30, 101}109. Kobe, K. A., & Hellwig, K. C. (1955). Sodium sul"te from caustic cell liquor. Industrial and Engineering Chemistry, 47, 1116}1121. Krissmann, J., Siddiqi, M., & Lucas, K. (1997). Absorption of sulfur dioxide in dilute aqueous solutions of sulfuric and hydrochloric acid. Fluid Phase Equilibria, 141, 221}233. Labash, J. A., & Lusby, G. R. (1955a). The reciprocal salt-pair system: NaCl}(NH ) SO }Na SO }NH Cl}H O at 203C and 603C.       Canadian Journal of Chemistry, 33, 774}786. Labash, J. A., & Lusby, G. R. (1955b). The reciprocal salt-pair system: NaCl}(NH ) SO }Na SO }NH Cl}H O at 203C and 603C.       Canadian Journal of Chemistry, 33, 787}796. Lantzke, R., Covington, A., & Robinson, R. (1972). Osmotic and activity coe$cients of sodium dithionate and sodium sul"te at 253C. Journal of Chemical Engineering Data, 17, 421}422. Llewellyn, D., & Currie, A. (1925). The system sodium sul"te}sodium hydroxide}water. Journal of Chemical Society, 127, 1623}1628. Maass, C., & Maass, O. (1928). Sulfur dioxide and its aqueous solutions. I. Analytical methods, vapor density and vapor pressure of sulfur dioxide. Vapor pressure and concentrations of the solutions. Journal of American Chemical Society, 50, 1352}1368. Morgan, O., & Maass, O. (1931). An investigation of the equilibria existing in gas}water systems forming electrolytes. Canadian Journal of Research, 5, 162}199. Morgan, R. (1961). Activity coe$cients of sodium sul"te in aqueous solution at 253C. Journal of Chemical Engineering Data, 6, 21}23. NIST Chemical Thermodynamics Database Version 1.1, (1990). US department of commerce, National Institute of Standard and Technology, Gaithesburg MD 20899. Parkinson, R. (1956). The solubility of sulfur dioxide in water and sulfuric acid. TAPPI, 39, 517}519. Platt, J. H., & Hudson, D. (1926). Solubility of potassium bisul"te. Journal of the Society of Dyers and Colourists, 348, 348}349. Rabe, A., & Harris, J. (1963). Vapor liquid equilibrium data for the binary system, sulfur dioxide and water. Journal of Chemical Engineering Data, 8, 333}336.

Fig. 8. Salt solubility in the (NH ) SO }(NH ) S O }(NH ) SO }        water system at 303C.

standard state properties and the parameters in Tables 3}5 should be used together.

Acknowledgements S. Pereda gratefully acknowledges the "nancial support of the ALFA program within the EU for the stay at DTU, Denmark.

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