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Fluid Phase Equilibria 167 2000. 263284 www.elsevier.

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Solubility of hydrogen sulfide in aqueous solutions of single strong electrolytes sodium nitrate, ammonium nitrate, and sodium hydroxide at temperatures from 313 to 393 K and total pressures up to 10 MPa
Jianzhong Xia, Alvaro Perez-Salado Kamps, Bernd Rumpf, Gerd Maurer
Received 16 August 1999; accepted 17 November 1999
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Lehrstuhl fur Technische Thermodynamik, Uniersitat Kaiserslautern, D-67653 Kaiserslautern, Germany

Abstract New experimental results for the solubility of hydrogen sulfide in aqueous solutions of the single strong electrolytes sodium nitrate, ammonium nitrate, and sodium hydroxide at temperatures from 313 to 393 K and total pressures up to 10 MPa are reported. As in the strong electrolyte-free system, a second hydrogen sulfide-rich liquid phase is observed at high hydrogen sulfide concentrations. A thermodynamic model for describing the phase equilibrium is presented. Calculations are compared with the new experimental data. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: Gas solubility; Experimental data; Vaporliquid equilibrium; Aqueous solutions; Electrolytes; Hydrogen sulfide; Sodium nitrate; Ammonium nitrate; Sodium hydroxide

1. Introduction The solubility of weak electrolyte gases like ammonia, carbon dioxide, sulfur dioxide, or hydrogen sulfide in aqueous solutions containing strong electrolytes strong acids and bases and their salts. must be known for designing separation equipment in many technical applications e.g., in the chemical or oil related industries and in the field of environmental protection. . In many cases, the correlation and prediction of vapor liquid equilibrium in such systems is an extremely difficult task, caused partially by chemical reactions in the liquid phase as well as by the possible formation of additional solid or

Corresponding author. Tel.: q49-631-205-2410; fax: q49-631-205-3835. E-mail address: gmaurer@rhrk.uni-kl.de G. Maurer..

0378-3812r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 8 - 3 8 1 2 9 9 . 0 0 3 2 4 - 6

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Table 1 Experimental results for the solubility of hydrogen sulfide in aqueous solutions of sodium nitrate T K. 313.15 313.15 313.16 313.14 313.16 313.17 313.14 313.15 313.16 313.16 333.14 333.14 333.15 333.13 333.15 333.14 333.15 333.15 353.16 353.16 353.16 353.16 353.16 353.16 353.17 353.16 393.15 393.17 393.17 393.17 393.16 393.16 393.19 393.16 393.17 393.17 313.15 313.15 313.17 313.14 313.14 313.15 313.14 313.16 313.16 313.13 313.15 m H 2 S molrkg. 0.088 0.210 0.426 0.469 0.690 0.815 0.946 1.255 1.776 1.820 0.031 0.164 0.404 0.842 1.320 1.596 1.811 2.230 0.087 0.360 0.384 0.834 1.220 1.767 1.918 2.723 0.000 0.123 0.324 0.884 1.181 1.371 1.512 1.763 1.857 1.969 0.064 0.159 0.539 0.838 0.952 1.407 1.528 1.808 0.171 0.336 0.502 m NaNO 3 molrkg. 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 3.040 5.866 5.866 5.866 5.866 5.866 5.866 5.866 5.866 5.952 5.952 5.952 10 p MPa. 1.618 3.746 7.64 8.35 12.27 14.62 16.92 22.80 28.29 28.29 1.053 4.050 9.66 20.24 32.71 40.89 42.72 42.72 3.077 10.93 11.83 25.52 37.94 58.82 61.68 61.68 1.780 6.69 14.84 36.50 49.01 57.93 62.16 71.57 84.21 91.06 1.607 3.722 11.69 18.62 21.18 28.34 28.37 28.36 3.785 7.55 11.08

p
2 2 2 2 2 2 2 2 3 3 2 2 2 2 2 2 3 3 2 2 2 2 2 2 3 3 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 3 3 3 2 2 2

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Table 1 continued . T K. 313.15 333.13 333.14 333.15 333.17 333.15 333.15 333.14 333.14 333.14 353.17 353.16 353.16 353.17 353.16 353.15 353.15 353.17 353.16 393.16 393.16 393.18 393.16 393.16 393.19 393.17 393.16 393.15 m H 2 S molrkg. 0.992 0.073 0.141 0.423 0.439 0.868 1.181 1.279 1.445 1.674 0.080 0.290 0.409 0.672 0.944 1.367 1.523 1.605 1.652 0.000 0.057 0.219 0.365 0.670 0.671 1.069 1.491 1.724 m NaNO 3 molrkg. 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 5.952 10 p MPa. 22.50 2.284 4.397 12.28 12.88 25.65 37.67 42.68 42.75 42.97 3.383 10.58 14.86 24.24 35.03 54.26 61.55 61.89 61.86 1.629 4.447 11.87 18.97 33.32 33.56 54.77 79.37 93.93

p
2 2 2 2 2 2 2 3 3 3 2 2 2 2 2 2 3 3 3 2 2 2 2 2 2 2 2 2

liquid phases. As part of ongoing projects dealing with that kind of phase equilibria, this contribution reports on experimental and theoretical results on the solubility of hydrogen sulfide in aqueous solutions of the single strong electrolytes sodium nitrate, ammonium nitrate, and sodium hydroxide at temperatures from 313 to 393 K, total pressures up to 10 MPa, and molalities of the strong electrolytes up to 6 m. For these systems, no similar data are available in the literature.

2. Experimental The experimental equipment and procedure are the same as in previous investigations see for example, Rumpf and Maurer w1x., therefore only a few essentials are repeated here. In an experiment, a thermostated high-pressure cell material: Hastelloy C4; volume: about 30 cm3 . with two sapphire windows is partially filled with a known amount of the aqueous solvent. A known amount of gas is added to the cell from a storage tank. More aqueous solvent is added to the cell by a calibrated high-pressure displacer, until the gas is completely dissolved in the liquid phase. The

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amount of solvent charged to the cell is only slightly above the minimum amount needed to dissolve the gas completely. After equilibration, very small amounts of the liquid mixture are withdrawn stepwise from the cell until the first very small stable bubble appears. That pressure is the equilibrium pressure to dissolve the charged amount of hydrogen sulfide in the charged amount of solvent at the fixed temperature. The mass of the charged gas up to about 3.6 g. is determined by weighing with an uncertainty of "0.008 g. The volume of the aqueous solvent needed to dissolve the gas is determined by measuring the position of the high-pressure displacer piston before and after each experiment. The mass of the solvent is calculated with a relative uncertainty of 0.7% at maximum. from its known density either from Washburn w2x or from own measurements. . Three pressure transducers WIKA, Klingenberg, Germany. for pressures ranging to 0.6 MPa, to 4 MPa and to 10 MPa, respectively, were used to determine the solubility pressure. Before and after each series of measurements, the transducers were calibrated against a high precision pressure gauge Desgranges & Huot, Aubervilliers, France. . The maximum uncertainty in the pressure measurement is about 1 kPa in the pressure range up to 0.5 MPa and 4 kPa at higher pressures. The temperature is determined with two calibrated platinum resistance

Table 2 Experimental results for the solubility of hydrogen sulfide in aqueous solutions of ammonium nitrate T K. 313.15 313.14 313.16 313.14 313.15 313.15 313.15 313.15 313.16 313.16 313.15 353.16 353.15 353.15 353.15 353.16 353.15 353.15 353.16 393.15 393.16 393.16 393.16 393.15 393.16 393.16 393.15 m H 2 S molrkg. 0.253 0.435 0.531 0.569 0.602 1.006 1.931 1.972 2.011 2.940 3.111 0.192 0.469 1.273 1.274 1.991 2.162 2.784 3.514 0.000 0.205 0.406 1.013 1.022 1.620 2.268 2.464 m NH 4 NO 3 molrkg. 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 5.790 10 p MPa. 3.198 5.492 6.98 7.29 7.60 12.73 24.34 24.80 25.52 28.46 28.46 4.77 11.06 28.96 28.90 46.89 51.85 62.39 62.36 1.663 8.23 14.74 34.39 34.45 54.95 77.06 83.25

p
2 2 2 2 2 2 2 2 2 3 3 2 2 2 2 2 2 3 3 2 2 2 2 2 2 2 2

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Table 3 Experimental results for the solubility of hydrogen sulfide in aqueous solutions of sodium hydroxide T K. 313.14 313.21 313.15 313.15 313.14 313.15 313.15 313.15 313.15 313.15 313.17 333.16 333.15 333.16 333.16 333.15 333.16 333.15 333.15 333.15 353.15 353.15 353.15 353.15 353.15 353.15 353.15 353.16 353.15 353.15 353.15 393.16 393.16 393.15 393.15 393.15 393.16 393.15 393.17 393.16 393.16 313.15 313.15 313.19 313.16 313.16 m H 2 S molrkg. 0.992 1.028 1.231 1.633 1.758 2.075 2.326 2.606 2.656 3.042 3.254 0.849 1.206 1.396 1.481 2.043 2.373 2.623 3.139 3.319 0.911 1.068 1.393 1.855 2.221 2.259 2.571 2.965 3.214 3.217 3.364 0.000 0.895 0.985 1.089 1.337 1.916 2.366 2.724 3.121 3.115 1.198 1.850 2.248 2.510 2.601 m NaOH molrkg. 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 0.993 1.957 1.957 1.957 1.957 1.957 10 p MPa. 0.459 1.157 4.701 11.57 13.33 19.11 23.59 28.51 28.49 28.51 28.50 0.197 5.140 9.15 10.75 23.91 32.16 40.05 43.02 43.03 0.473 3.195 11.59 25.22 36.08 37.20 47.39 58.96 62.43 62.43 62.45 1.905 1.933 2.557 5.804 15.61 38.17 55.81 71.85 92.50 92.96 0.151 0.205 5.717 10.73 12.83

p
2 2 2 2 2 2 2 2 3 3 3 2 2 2 2 2 2 2 3 3 2 2 2 2 2 2 2 2 3 3 3 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 continued on next page .

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Table 3 continued . T K. 313.14 313.15 313.14 313.15 313.14 313.14 313.16 313.15 313.15 313.15 333.14 333.14 333.15 333.17 333.14 333.16 333.16 333.14 333.14 333.14 353.16 353.15 353.15 353.16 353.16 353.16 353.15 353.16 353.15 353.16 393.16 393.17 393.15 393.16 393.14 393.14 393.14 393.16 393.14 393.15 m H 2 S molrkg. 2.643 2.653 3.256 2.260 2.649 2.874 3.334 3.526 3.948 3.962 2.202 2.276 2.670 2.929 3.043 3.355 3.601 3.652 3.757 4.071 1.919 2.228 2.577 2.720 2.760 3.050 3.638 3.695 4.386 4.469 0.000 1.541 2.204 2.495 2.584 2.688 3.236 3.280 3.660 3.878 m NaOH molrkg. 1.957 1.957 1.957 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 1.980 10 p MPa. 14.12 14.34 26.78 6.46 13.58 18.31 27.66 28.42 28.47 28.55 5.95 7.65 16.74 23.27 27.01 35.86 43.09 43.07 43.08 43.08 0.477 8.14 19.33 23.24 24.85 34.84 57.47 61.76 62.37 62.38 1.836 1.920 11.95 23.99 28.04 32.41 56.89 59.23 78.96 93.19

p
2 2 2 2 2 2 2 3 3 3 2 2 2 2 2 2 3 3 3 3 2 2 2 2 2 2 2 2 3 3 2 2 2 2 2 2 2 2 2 2

thermometers placed in the heating jacket of the cell with an estimated maximum uncertainty of about "0.1 K. The strong electrolyte-containing solutions were prepared in a storage tank. The molality of the strong electrolyte in the aqueous solution was determined gravimetrically with a relative uncertainty not surmounting 0.1%.

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3. Substances Hydrogen sulfide G 98 mol%. was purchased from Messer-Griesheim, Ludwigshafen, Germany, and was used without further purification. Deionized water was degassed by vacuum distillation. Sodium nitrate G 99.5 mass%. , ammonium nitrate G 99 mass%. and sodium hydroxide G 99 mass%. were purchased from Riedel de Haen, Seelze, Germany, and were degassed and dried under vacuum.

4. Experimental results The solubility of hydrogen sulfide in aqueous solutions of sodium nitrate m NaNO3 f 3 and 6 molrkg. and sodium hydroxide m NaOH f 1 and 2 molrkg. was measured at 313, 333, 353, and 393 K. The solubility of hydrogen sulfide in aqueous solutions of ammonium nitrate m NH 4 NO3 f 6 molrkg. was measured at 313, 353, and 393 K. The total pressure ranged up to about 10 MPa. The experimental results are given in Tables 13. For all investigated systems, the formation of a second, hydrogen sulfide-rich liquid phase was observed at higher concentrations of hydrogen sulfide. Therefore, the number of observed phases p . is also given in Tables 13. When there are three phases, the number given for m H 2 S in Tables 13 and also in the corresponding figures. is no longer

Fig. 1. Solubility of hydrogen sulfide in aqueous solutions of sodium nitrate at T s 353 K. `,I Experimental results, this work. Calculated results, this work. - - - Calculated results for the system H 2 SH 2 O.

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the solubility of H 2 S in the aqueous solution, as all numbers for m H 2 S are the ratio of moles of. hydrogen sulfide to kilograms of. water in the equilibrium cell. As an example, the experimental results for the total pressure above aqueous solutions containing about 3 and 6 mol of NaNO 3 per kg of H 2 O at 353 K are plotted in Fig. 1 versus the overall amount of hydrogen sulfide per kilogram of water in the equilibrium cell. Adding hydrogen sulfide to an aqueous salt solution at first causes a nearly linear increase in the total pressure until a second, hydrogen sulfide-rich liquid phase appears. The presence of NaNO 3 has almost no influence on the pressure of the three-phase vaporliquidliquid equilibrium. Hydrogen sulfide is salted out by sodium nitrate. The salting out effect increases with increasing salt molality. For example, when 3 or 6 mol of sodium nitrate are added to 1 kg of water at 353 K, the pressure needed to dissolve 1 mol of hydrogen sulfide increases from about 2.5 MPa to about 3.1 and 3.9 MPa, respectively. Vice versa, at a total pressure of 3.9 MPa, the hydrogen sulfide molality is about 1.6 molrkg in pure water, whereas it is about 1.2 and 1.0 molrkg in a 3- and 6-m aqueous solution of sodium nitrate, respectively. Another example: when 3 or 6 mol of sodium nitrate are added to 1 kg of water at 353 K, the molality of hydrogen sulfide required to induce a phase split is reduced from about 2.3 molrkg to about 1.8 and 1.5 molrkg, respectively. Fig. 2 shows the influence of 6 mol sodium nitrate and ammonium nitrate per kilogram of water on the solubility of hydrogen sulfide in an aqueous solution at 353 K. In contrast to the salting-out effect caused by sodium nitrate, ammonium nitrate causes a salting-in effect. For example: the pressure necessary to dissolve 1 mol of hydrogen sulfide in 1 kg of water increases from about 2.5 MPa to

Fig. 2. Solubility of hydrogen sulfide in aqueous solutions of sodium and ammonium nitrate at T s 353 K. `,I Experimental results, this work. Calculated results, this work. - - - Calculated results for the system H 2 SH 2 O.

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Fig. 3. Solubility of hydrogen sulfide in aqueous solutions of sodium hydroxide. ` Experimental results, this work, m NaOH s 1 molrkg. Predictions, this work.

about 3.9 MPa in the presence of sodium nitrate, whereas it decreases to about 2.35 MPa if ammonium nitrate is present. As was to be expected, the addition of hydrogen sulfide to a solution containing a fixed overall molality of the strong base sodium hydroxide cf. Fig. 3. at first results only in a slight change in the total pressure, as nearly all hydrogen sulfide is dissolved in ionic form, i.e., as bisulfide and sulfide. ions. When the overall amount of hydrogen sulfide in the liquid phase nearly equals the overall amount of sodium hydroxide, the total pressure above the aqueous solution steeply increases. As in the system hydrogen sulfidewater, the solubility decreases with increasing temperature. As can also be seen from Figs. 1 and 2, the pressure at the three-phase equilibrium is the same in the salt-free system as in the salt containing systems. This indicates that the second liquid phase is nearly pure hydrogen sulfide.

5. Modeling 5.1. Systems H2 SH2 ONaNO3 and H2 SH2 ONH4 NO3 Fig. 4 shows a scheme of the model applied to correlate the new data. At the concentrations discussed here, the dissociation of dissolved hydrogen sulfide in the aqueous phase can be neglected. However, for very small amounts of dissolved hydrogen sulfide the dissociation of H 2 S and HSy can

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y. Fig. 4. VLLE in the system H 2 SH 2 OMnq Xny M s Naq or NHq 4 , X s NO 3 .

be taken into account cf. Section 5.2.. It is assumed that the salts sodium nitrate and ammonium nitrate are fully dissociated in the aqueous phase. The second hydrogen sulfide-rich. liquid phase and the vapor phase are treated as binary mixtures of hydrogen sulfide and water. 5.1.1. Vaporliquid equilibrium The vaporliquid equilibrium conditions for water and hydrogen sulfide are:
s pw

w exp

s w

s w p y pw .

RT

Z aXw s pyw ww

1.
m ., mXH 2 Sg H s py H 2 S w Z H2S . 2S
X

m . HH 2 S,w

s T , pw

. exp

s ` H 2 S,w p y pw .

RT

2.

m . s . HH T , pw denotes Henrys constant for the solubility of hydrogen sulfide in pure water. It was 2 S,w adopted from Edwards et al. w3x cf. Table 4. . The influence of pressure on that Henrys constant was estimated using the partial molar volume of hydrogen sulfide in water as given by Brelvi and OConnell w4x cf. Table 5. . The vapor pressure and molar volume of pure liquid water were calculated from the equations of Saul and Wagner w5x. Fugacity coefficients in the vapor phase were calculated from the virial equation of state truncated after the second virial coefficient. The second virial coefficient of pure water Bw,w was calculated from a correlation based on the data collection by

Table 4 Henrys constant of hydrogen sulfide in pure water m . s HH B T , pw . 2 S,w ln s Aq q C T rK . q D ln T rK . y1 T r K. MPa kg mol . A 340.292 B y13236.8 C 0.0595651 D y55.0551

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Table 5 Pure component and mixed second virial coefficients, partial molar volumes of H 2 S at infinite dilution in water T K. 313.15 333.15 353.15 393.15 B H 2 S,H 2 S cm3rmol. y182 y162 y145 y118 BH 2 S,w cm3rmol. y381 y318 y270 y203 3 . ` H 2 S,w cm rmol 35.9 37.2 38.9 43.7

Dymond and Smith w6x cf. Table 6. . The second virial coefficient of pure hydrogen sulfide B H 2 S,H 2 S and the mixed second virial coefficient BH 2 S,w were estimated as recommended by Hayden and OConnell w7x cf. Table 5.. A modified Pitzer model w8x for the excess Gibbs energy of aqueous solutions containing strong electrolytes is applied to calculate the activities of all species in the liquid phase: GE n w RTM w s f 1 I . q q

mi m j
i/ w j/ w

bi,0j. q bi,1j. f 2 x 1 . q bi,2j. f 2 x 2 .

m i m j m kt i , j , k .
i/ w j/ w k/ w

3.

The resulting expressions for the activity coefficient of a dissolved species and for the activity of water are given in Appendix A. f 1 and f 2 are functions of ionic strength I. The dielectric constant of pure water is required for calculating f 1 I .. It was taken from Bradley and Pitzer w9x. bi,0j ., bi,1j ., bi,2j ., and t i, j, k are binary and ternary interaction parameters. Interaction parameters for the binary system NaNO 3 H 2 O were taken from Sing et al. w10x, and for NH 4 NO 3 H 2 O from Kim and Frederick w11x cf. Appendix B. . According to Pitzers equation cf. Appendix A., the activity coefficient of a gas G molality m G . dissolved in pure water is
m . 0 . 2 lng G m s s 0 . s 2 m G bG ,G q 3 m Gt G ,G ,G ,

4.

whereas it is
m . 0 . 1 . 2 . 0 . 1 . lng G s 2 m G bG ,G q bG ,G f 2 x 1 . q bG ,G f 2 x 2 . q 2 m s BG ,MX q BG ,MX f 2 x 1 . 2 . 2 2 qBG ,MX f 2 x 2 . q 3 m Gt G ,G ,G q 3 m s GG ,MX ,MX q 6 m G m s GG ,G ,MX

5.

in an aqueous solution containing a strong electrolyte MnqX ny salt molality m s ..


Table 6 Pure component second virial coefficient of water d c Bw ,w r cm3rmol . s a q b T rK .

a y53.53

b y39.29

c 647.3

d 4.3

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0 . The binary parameter b H was taken from Kuranov et al. w12x cf. Table 7.. The ternary 2 S,H 2 S 0 . 1 . 2 . parameter t H 2 S,H 2 S,H 2 S was neglected. The parameters BG,MX , BG,MX , BG,MX , GG,G,MX and GG,MX,MX are combinations of the second and third virial coefficients and are given by: i. i. i. BG ,MX s nq bG ,M q ny bG ,X

i s 0,1,2

6. 7. 8.

2 2 GG ,MX ,MX s nq t G ,M ,M q 2 nq ny t G ,M ,X q ny t G ,X ,X

GG ,G ,MX s nq t G ,G ,M q ny t G ,G ,X .

1 . 2 . 1 . 2 . The parameters bG,G , bG,G , BG,MX , BG,MX , and GG,G,MX were neglected, i.e., they were set to zero.

5.1.2. System H2 SH2 ONaNO3 0 . 0 . The remaining parameters BG,MX and GG,MX,MX i.e., B H and G H 2 S,NaNO3,NaNO3 . were fitted 2 S,NaNO 3 to the new results for the total pressure above H 2 SH 2 ONaNO 3. For the parameter determination, only vaporliquid equilibrium data, i.e., no experimental data in the three-phase region were considered. The influence of temperature on the interaction parameters was expressed by q2, i f T . s q1, i q . 9. TrK. The resulting numbers for q1, i and q2, i are given in Table 7. 5.1.3. System H2 SH2 ONH4 NO3 0 . The following expression for BH is obtained by applying Eq. 6. to the systems 2 S,NH 4 NO 3 H 2 SH 2 Osalt, with single salts Na 2 SO4 , NH 4 . 2 SO4 , NaNO 3 , and NH 4 NO 3:
0 . BH s 2 S,NH 4 NO 3

1 2

0 . 0 . 0 . BH y BH q BH . 2 S, NH 4 . 2 SO 4 2 S ,Na 2 SO 4 2 S ,NaNO 3

10.

0 . 0. 0 . BH and BH were taken from Xia et al. w13x. BH was taken from the 2 S,Na 2 SO4 2 S,NH 4 . 2 SO 4 2 S,NaNO 3 0 . correlation presented above. Thus BH 2 S,NH 4 NO3 was predicted.

Table 7 Interaction parameters for Pitzers equation for the systems H 2 SNaNO 3 H 2 O, H 2 SNH 4 NO 3 H 2 O and H 2 SNaOH H 2O q2, i f T . s q1, i q T rK. Parameter
0 . bH 2 S,H 2 S 0 . B H 2 S,NH 4 HS 0 . BH 2 S,Na 2 SO4 0 . BH 2 S,NH 4 . 2 SO 4 0 . BH 2 S,NaNO 3

q1, i y0.26156 0.05147 y0.08436 0.14091 0.00163 y2=10y5 0.114265 1.16=10y3

q2, i 69.751 y21.2928 115.72732 4.70824 10.45166 y45.05788

T rK 283453 313393 313393 313393 313393 313393

Subsystem H 2 SH 2 O NH 3 H 2 SH 2 O H 2 SH 2 ONa 2 SO4 H 2 SH 2 O NH 4 . 2 SO4 H 2 SH 2 ONaNO 3 H 2 SH 2 ONH 4 NO 3

Source Kuranov et al. w12x Rumpf et al. w15x Xia et al. w13x Xia et al. w13x fitted this work. prediction from Eq. 10. fitted this work.

G H 2 S,NaNO 3 ,NaNO 3 0 . BH 2 S,NH 4 NO 3 G H 2 S,NH 4 NO 3 ,NH 4 NO 3

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Table 8 Distribution coefficients of hydrogen sulfide and water in H 2 SH 2 O g 2, i ,X ln K Y i s g1 ,i q T rK. i H2S H 2O g 1, i y1.0711 3.44803 g 2, i 173.1356 y2429.741

The ternary parameter G H 2 S,NH 4 NO3,NH 4 NO3 cannot be calculated in a similar way. This parameter was fitted to the new experimental results for the total pressure above H 2 SH 2 ONH 4 NO 3. Only vaporliquid but no vaporliquidliquid equilibrium data were considered for determining that parameter. The parameters are given in Table 7. 5.1.4. Vaporliquidliquid equilibrium The phase equilibrium between the coexisting liquid phases is expressed by:
X K iY , s X

ai

aXi

s exp

, , mref y mref i i

RT

i s H 2 S, H 2 O

11 .

where K iY , is the distribution coefficient of component i either hydrogen sulfide or water. between the water-rich X . and the hydrogen sulfide-rich Y . phases. In the hydrogen sulfide-rich phase, concentrations are expressed through mole fraction and the unsymmetric convention for normalization is chosen: For hydrogen-sulfide, the reference state is the Y ref, Y . pure liquid mref, H 2 S s m H 2 S T , p pure liquid ; for water, it is the infinitely diluted solution m w s ` m w,H 2 S T , p .. As the second liquid phase is nearly pure hydrogen sulfide, it is assumed that this phase behaves like an ideal solution. Therefore, the activities of hydrogen sulfide and water were replaced by the mole fractions: a i Y s xY i i s H 2 S, H 2 O.

12 .

X The distribution coefficients K iY , were taken from Xia at al. w13x cf. Table 8..

5.2. System H2 SH2 ONaOH Fig. 5 shows a scheme of the model applied to predict the solubility of hydrogen sulfide in aqueous solutions of sodium hydroxide. Here, the chemical reactions in the liquid phase, which convert hydrogen sulfide to bisulfide and sulfide ions as well as the autoprotolysis of water have to be taken into account. H 2S

| H q HS HS | H q S H O | H q OH
q y q 2y q 2

R1. R2. R3.

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Fig. 5. VLLE in the system H 2 SH 2 ONaOH.

Sodium hydroxide is assumed to be present only in the aqueous phase, where it is completely dissociated. The second hydrogen sulfide-rich. liquid phase and the vapor phase are treated as binary mixtures of hydrogen sulfide and water. 5.2.1. Vaporliquid equilibrium The condition for chemical equilibrium yields the following equation for a chemical reaction R: K R T . s a i n i ,R .
i

13.

The balance equations for the overall number of moles of sodium hydroxide, hydrogen sulfide, and water result in: n NaOH s nXNaq , n H 2 S s nXH 2 S q nXHSy q nXS2y , n H 2 O s nXH 2 O q nXOHy y nXNaq . The condition for electroneutrality of the aqueous phase gives: nXHq q nXNaq s nXOHy q nXHSy q 2 nXS2y .

14 . 15. 16.

17 .

Solving this set of equations for given temperature and overall mole numbers n i of components i.e., H 2 S, H 2 O and NaOH. results in the true composition of the liquid phase, i.e., the molalities of true species i. The conditions of vaporliquid equilibrium between the aqueous phase and the gas phase cf. Eqs. 1. and 2.. can then be applied to calculate the total pressure and the composition of the gas phase. Apart from the information already given in Section 5.1, the calculation requires the knowledge of the temperature-dependent equilibrium constants K 1 K 3 , which were taken from Edwards et al. w3x

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277

Table 9 Chemical equilibrium constants AR ln K R s q BR ln T rK . q C R T rK . q D R T rK. Reaction H2S HSy H 2O

| HS qH | S qH | H qOH
y 2y q

AR y18034.72 y406.0035 y13445.9

BR y78.07186 33.88898 y22.4773

C R =10 2 9.19824 y5.411082 0

DR 461.7162 y214.5592 140.932

q y

cf. Table 9.. Activity coefficients were calculated from the G E equation of Pitzer w8x. Parameters describing interactions in H 2 SH 2 ONaOH can be divided into different groups. 1. Interaction parameters for the binary subsystem H 2 SH 2 O. They were taken from Kuranov et al. w12x cf. Table 7.. 2. Interaction parameters for the binary subsystem NaOHH 2 O. They were taken from Pabalan and Pitzer w14x cf. Table 10 and Appendix B.. 3. The following parameters were determined by Rumpf et al. w15x from VLE data in the ternary 0 . 0 . 1 . q y, b y , and t q y. According to Eq. 6. : system NH 3 H 2 SH 2 O: B H , b NH NHq NHq 2 S,NH 4 HS 4 ,HS 4 ,HS 4 ,NH 4 ,HS 0 . 0 . 0 . y BH 2 S,NH 4 HS s b H 2 S,NHq q b H 2 S,HSy . As in this system the concentrations of NHq ions are 4 and HS 4 0 . q was arbitrarily set to zero without losing any generality, practically the same, b H S,NH 2 4
0 . qs0 bH 2 S,NH 4

18.

and consequently cf. Table 7.:


0 . 0 . ysB bH H 2 S,NH 4 HS . 2 S,HS 0 . 0 . 0 . 4. b H . . q was determined from B H 2 S,NaNO 3 and B H 2 S,NH 4 NO 3 with Eqs. 6 and 18 : 2 S,Na 0 . 0 . 0 . qsB bH H 2 S,NaNO 3 y B H 2 S,NH 4 NO 3 . 2 S,Na

19.

20.

5. Due to the very small amounts of Hq ions, all interaction parameters involving this species were set to zero. 6. As the equilibrium constant for the formation of S 2y ions reaction R2.. is rather small, all interaction parameters involving this species were set to zero. 7. All interaction parameters involving only charged species of the same sign were neglected. 0 . 0 . 8. There remain two unknown binary parameters: b H y q and b Na ,HSy . When both are 2 S,OH . neglected i.e., set to zero , the model can be used to predict the solubility of H 2 S in aqueous NaOH. 0 . y y causes no serious problems, as H S and OH Neglecting b H never appear simultaneously in 2 2 S,OH high concentrations. This is demonstrated in Fig. 6, where the predictions for the true molalities of all the important species in an aqueous solution of 1 mol of NaOH at 313 K are plotted versus the overall molality of H 2 S.

278

J. Xia et al. r Fluid Phase Equilibria 167 (2000) 263284

Fig. 6. Predictions for the aqueous phase molalities of the most important species in the system H 2 SH 2 ONaOH at 313.15 K and m NaOH s 1 molrkg.

5.2.2. Vaporliquidliquid equilibrium The same procedure was applied as for the systems H 2 S q H 2 O q NaNO 3 or NH 4 NO 3 . , allowing a prediction of pressure and compositions of the coexisting phases.

Fig. 7. Solubility of hydrogen sulfide in a 6-m aqueous solution of sodium nitrate. ` Experimental results, this work. Calculated results, this work.

J. Xia et al. r Fluid Phase Equilibria 167 (2000) 263284

279

6. Comparison of experimental data with model calculations A comparison between the new experimental results for the total pressure and calculated results from the correlation for the system H 2 SH 2 ONaNO 3 see Fig. 7 for m NaNO3 f 6 molrkg. yields an average relative deviation of 3.2%. The maximum relative deviation in the total pressure is 15.6%, occurring at T s 333.14 K, and p s 0.1053 MPa, where the calculated pressure is too small by about 16 kPa. Typical relative deviations range from 1% to 4%. The model predicts the pressure at the three-phase-line VLLE. with an average relative deviation of 1.8%. The experimental results for the total pressure above H 2 SH 2 ONH 4 NO 3 are correlated with an average relative deviation of 9.3%. The maximum relative deviation is 16% corresponding to an absolute deviation of 0.112 MPa at T s 313.16 K, p s 0.698 MPa. . The average relative deviation between predicted and measured pressures at the three-phase line is 1.8%. Fig. 8 shows a comparison between the new experimental results for the total pressure above an aqueous solution containing about 6 mol of NH 4 NO 3 per kg of H 2 O and the results from the correlation. It is worthwhile to 0 . mention that the correlation can be improved by fitting BH together with G H 2 S,NH 4 NO3,NH 4 NO3 2 S,NH 4 NO 3 to the experimental data instead of predicting that parameter. The average relative deviation in the total pressure is then reduced from 9.3% to 1.9%. As can be seen from Fig. 3, for the system H 2 SH 2 ONaOH, a good agreement is achieved between the new experimental data and the prediction. The average relative deviation in the total

Fig. 8. Solubility of hydrogen sulfide in a 6-m aqueous solution of ammonium nitrate. ` Experimental results, this work. Calculated results, this work.

280

J. Xia et al. r Fluid Phase Equilibria 167 (2000) 263284

pressure is 8.8%. However, that deviation mostly results from a few data points at hydrogen sulfide molalities m H 2 S - m NaOH , where the total pressure is nearly not changed by the addition of hydrogen sulfide. In that low-pressure range, the absolute uncertainty in the pressure readings can reach up to 5%. The pressure at three-phase equilibrium VLLE. is predicted with an average relative deviation of about 2%.

7. Conclusions The solubility of hydrogen sulfide in aqueous solutions containing the single strong electrolytes sodium nitrate, ammonium nitrate and sodium hydroxide was measured at temperatures from 313 to 393 K, and total pressures up to 10 MPa. The salt molalities were about 3 and 6 for sodium nitrate, about 6 for ammonium nitrate, and about 1 and 2 for sodium hydroxide. The maximum ratio of hydrogen sulfide to water in the equilibrium cell was about 4.5 molrkg. In some experiments, the concentration was above the solubility limit for hydrogen sulfide and therefore, a second, hydrogen sulfide-rich liquid phase was observed. Thermodynamic models are used to describe the vaporliquid and vaporliquidliquid equilibria. Interaction parameters for Pitzers G E equation were determined from the new experimental results for the systems H 2 SH 2 ONaNO 3 and H 2 SH 2 ONH 4 NO 3. The model successfully predicts the pressures above H 2 SH 2 ONaOH within the experimental uncertainties. Furthermore, the model reliably predicts the three-phase VLLE. pressure. List of symbols a... d coefficients for the temperature dependence of second virial coefficients of water A... D coefficients for the temperature dependence of Henrys constant for the solubility of hydrogen sulfide in pure water AR . . . D R coefficients for the temperature dependence of chemical equilibrium constants Aw DebyeHuckel parameter ai activity of component i b constant in modified DebyeHuckel expression i. BG,MX effective second osmotic virial coefficient for interactions between a gas G and a salt MX i s 0,1,2. f third osmotic virial coefficient in Pitzers equation C D relative dielectric constant of water e charge of proton f function for the temperature dependence of an interaction parameter f 1, f 2 , f 3 functions in Pitzers equation gi coefficients for the temperature dependence of distribution coefficients G gas here hydrogen sulfide. E excess Gibbs energy G m. Hi,w Henrys constant for the solubility of gas i in pure water on molality scale. I ionic strength on molality scale. k Boltzmann constant Ki distribution coefficient

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281

KR M Mw mi mi ni ni NA p qi R T X x , x 1, x 2 y zi Greek letters a 1, a 2 b 0., b 1., b 2. g m . G 0 l i, j mi n i,R nq, ny p r t w Subscripts G i , j, k R s w Superscripts m. s `


X Y

equilibrium constant for chemical reaction R on molality scale. cation M molar mass of water kgrmol. overall molality of component i true molality of component i overall number of moles of component i in equilibrium cell true number of moles of component i Avogadros number pressure coefficients for the temperature dependence of interaction parameters universal gas constant absolute temperature partial molar volume anion X variables in Pitzers equations mole fraction in vapor number of charges of component i constants in Pitzers equation binary interaction parameters in Pitzers equation activity coefficient normalized to infinite dilution on molality scale. third osmotic virial coefficient vacuum permittivity second osmotic virial coefficient in Pitzers equation chemical potential of component i stoichiometric coefficient of component i in reaction R number of cations and anions in salt M nqX ny number of phases mass density ternary interaction parameter in Pitzers equation fugacity coefficient gas components i , j, k reaction R salt water on molality scale saturation infinite dilution water-rich liquid phase hydrogen sulfide-rich liquid phase

282
Z

J. Xia et al. r Fluid Phase Equilibria 167 (2000) 263284

ref

gas phase reference state

Acknowledgements Financial support of this investigation by the Volkswagen-Stiftung, Hannover, Germany Grant No. Ir70 877., as well as by the government of the Federal Republic of Germany BMFT Grant No. 0326558 C., and BASF AG, Ludwighafen; Bayer AG, Leverkusen; Degussa AG, Hanau; Hoechst AG, Frankfurt; Linde KCA, Dresden; and Lurgi AG, Frankfurt is gratefully acknowledged. J.X. thanks the Deutscher Akademischer Austauschdienst DAAD. for granting a scholarship.

Appendix A. Brief outline of Pitzers model The equation of Pitzer w8x for the excess energy of an aqueous, salt containing system is GE RTn w M w s f 1 I . q

m i m j l i , j I . q m i m j m kt i , j , k .
i/ w j/ w i/ w j/ w k / w

21.

f 1 I . is a modified DebyeHuckel term f 1 I . s yAw 4I b ln 1 q b'I .

22.

where I is the ionic strength Is 1 2

m i z i2 .
i

23 .

b is 1.2 kgrmol. 1r2 for all electrolytes. Aw is the DebyeHuckel parameter for the osmotic coefficient Aw s 1 3

2p NA r w .

0.5

e2 4p 0 DkT

1.5

24.

l i, j I . is the ionic strength dependent second virial coefficient: l i , j I . s bi,0j. q bi,1j. f 2 x 1 . q bi,2j. f 2 x 2 .
where bi,0j ., bi,1j . and bi,2j . are binary interaction parameters. The function f 2 is defined as f2 x . s 2 x2 1 y 1 q x . eyx

25.

26.

where x 1 s a 1'I and x 2 s a 2'I . For salts with at least one univalent cation or anion, a 1 has the value 2.0 and the binary parameter 2 . bi, j is usually set to zero except at very high temperatures.

J. Xia et al. r Fluid Phase Equilibria 167 (2000) 263284

283

Table 10 Ion interaction parameters for aqueous solutions of NaNO 3 and NH 4 NO 3 TR f T . s q1 q q2 1y T

Salt NaNO 3

Parameter

q1 0.00388 0.21151 y0.00006 y0.01476 0.13826 0.00029

q2 0.04938 8.6493 y0.0003

Source Sing et al. w10x

NH 4 NO 3

b 0 . b 1 . Cf b 0. b 1 . Cf

Kim and Frederick w11x

Differentiation of Eq. 21. yields the activity coefficient of a dissolved species i: lng i m . s yAw z i2 y z i2 where f 3 is f3 x . s 1 Ix 2 1y 1qxq

'I
1 q b'I q

2 b

ln 1 q b'I . q 2

mj
j/ w

bi,0j. q bi,1j. f 2 x 1 . q bi,2j. f 2 x 2 .

m j mk
j/ w k/ w

b j,1k. f 3 x 1 . q b j,2k. f 3 x 2 . q 3

m j m kt i , j , k .
j/ w k / w

27.

x2 2

eyx .

28.

Table 11 Ion interaction parameters for aqueous solutions of NaOH Pabalan and Pitzer w14x. f T . s q1 q q2 p q q3 q q4 p . r T q q5 lnT q q6 q q 7 p . T q q8 q q9 p . T 2 q q10 q Cf y1.6686897=10 1 4.0534778=10y 4 4.5364961=10 2 y5.1714017=10y 2 2.9680772 y6.5161667=10y 3 y1.05530373=10y 6 2.3765786=10y 6 8.9893405=10y 10 y6.8923899=10y 1 y8.1156826=10y 2 0.0 q11 q q12 p

T y227.

647y T .

b 0.
q1 q2 q3 q4 q5 q6 q7 q8 q9 q10 q11 q12 2.7682478=10 2 y2.8131778=10y 3 y7.3755443=10 3 3.7012540=10y 1 y4.9359970=10 1 1.0945106=10y 1 7.1788733=10y 6 y4.0218506=10y 5 y5.8847404=10y 9 1.1931122=10 1 2.4824963 y4.821740=10y 3

b 1 .
4.6286977=10 2 0.0 y1.0294181=10 4 0.0 y8.5960581=10 1 2.3905969=10y 1 0.0 y1.0795894=10y 4 0.0 0.0 0.0 0.0

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J. Xia et al. r Fluid Phase Equilibria 167 (2000) 263284

The activity of water follows from the GibbsDuhem equation ln a w s M w 2 Aw I 1.5 1 q b'I y

m i m j bi ,j0 . q bi ,j1 . ey x q bi ,j2 . ey x /


1 2

i/ w j/ w

y2

m i m j m kt i , j , k y m i
i/ w j/ w k/ w i/ w

29.

For systems containing a single salt MnqX ny, the binary and ternary parameters involving two or more species of the same sign of charge are usually set to zero. The ternary parameters t M,X,X , t M,M,X are usually reported as third virial coefficients C f for the osmotic coefficient: 1 3 C s
f

/
ny

nq

1 2

t M ,M ,X q

/
nq

ny

1 2

t M ,X ,X .

30.

Instead of rewriting Eqs. 27. and 29. in terms of C f , we preferred to set t M,X,X to zero and calculated the ternary parameter t M,M,X from the reported values for C f : 1:1 salt: 1 t M ,M ,X s C f 3

31.

Appendix B. Interaction parameters for Pitzers equation Literature data for the temperature dependent ionic interaction parameters b 0., b 1. and C f for the systems NaNO 3 q H 2 O, NH 4 NO 3 q H 2 O, and NaOH q H 2 O are given in Tables 1011. T is the temperature in kelvin TR s 298.15 K.. p is the pressure in bar. In the present work, for the calculation of interaction parameters, p was approximated by the saturation pressure of pure water.

References
w1x w2x w3x w4x w5x w6x w7x w8x w9x w10x w11x w12x w13x w14x w15x B. Rumpf, G. Maurer, Fluid Phase Equilib. 81 1992. 241260. E.W. Washburn, International Critical Tables of Numerical Data, McGraw-Hill, New York, 1928. T.J. Edwards, G. Maurer, J. Newman, J.M. Prausnitz, AIChE J. 24 1978. 966976. S.W. Brelvi, J.P. OConnell, AIChE J. 18 1972. 12391243. A. Saul, W. Wagner, J. Phys. Chem. Ref. Data 16 1987. 893901. J.H. Dymond, E.B. Smith, The Virial Coefficients of Pure Gases and Mixtures, Oxford Univ. Press, Oxford, UK, 1980. J.G. Hayden, J.P. OConnell, Ind. Eng. Chem. Proc. 14 1975. 209216. K.S. Pitzer, J. Phys. Chem. 77 1973. 268277. D.J. Bradley, K.S. Pitzer, J. Phys. Chem. 83 1979. 15991603. R. Sing, B. Rumpf, G. Maurer, Ind. Eng. Chem. Res. 38 1999. 20982109. H.T. Kim, W.J. Frederick Jr., J. Chem. Eng. Data 33 1988. 177184. G. Kuranov, B. Rumpf, N. Smirnova, G. Maurer, Ind. Eng. Chem. Res. 35 1996. 19591966. Perez-Salado J. Xia, A. Kamps, B. Rumpf, G. Maurer, Ind. Eng. Chem. Res., in press. R.T. Pabalan, K.S. Pitzer, Geochim. Cosmochim. Acta 51 1987. 829837. Perez-Salado B. Rumpf, A. Kamps, R. Sing, G. Maurer, Fluid Phase Equilib. 158160 1999. 923932.

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