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**Use of Hydration and Dissociation Chemistries
**

with the Electrolyte–NRTL Model

Chau-Chyun Chen, Paul M. Mathias, and Hasan Orbey

Aspen Technology, Inc., Cambridge, MA 02141

**Sound theoretical understanding and accurate mathematical representation of elec-
**

trolyte solution nonideality were the subject of extensi®e research efforts for decades. It is

demonstrated that these goals can be achie®ed by incorporation of hydration and partial

dissociation chemistries with the semi-empirical electrolyte NRTL model. The resulting

model pro®ides a comprehensi®e thermodynamic framework for accurate correlation

and reliable extrapolation of electrolyte solution nonideality o®er the entire concentra-

tion range.

Introduction

Reliable design and operation of industrial processes in- interactions among various species in electrolyte solutions.

volving electrolytes require sound theoretical understanding Consequently, the model has been widely applied to corre-

and accurate mathematical representation of the solution late electrolyte systems encountered in the chemical industry

nonideality of aqueous electrolyte systems. Many theories and ŽAspen Technology, Inc., 1998.. For some aqueous elec-

engineering models have been proposed, and they are well trolyte systems, however, such as HCl, LiCl, MgCl 2 , and

summarized by Zemaitis et al. Ž1986., Loehe and Donohue CaCl 2 , for which the nonideality in the high-concentration

Ž1997., and others. Among the successful engineering corre- range is particularly large, the extrapolations from the NRTL

lations are the models of Meissner and Tester Ž1972., Pitzer model for mean ionic activity coefficients of electrolytes are

Ž1973., Bromley Ž1973., and the electrolyte nonrandom two- found to be much lower than experimental values ŽAbovsky

liquid ŽNRTL. model of Chen et al. Ž1982. and Chen and et al., 1998.. There have been a number of attempts to im-

Evans Ž1986.. prove the performance of the NRTL model ŽHaghtalab and

While existing engineering models are found to describe Vera, 1988, 1991; Liu and Gren, 1991.. Most recently,

well the nonideality of aqueous electrolytes at relatively low Abovsky et al. Ž1998. proposed the inclusion of concentration

concentrations, they often inaccurately represent the solution dependence of interaction parameters ‘‘in order to enhance

nonideality at high concentrations. For example, both the the capability of the model in representing the nonideality of

Pitzer and the Bromley models cover electrolyte concentra- concentrated electrolyte solutions.’’

tions only up to 6 molal. Much empiricism and data fitting Thermodynamically rigorous modeling of electrolyte solu-

are needed to extend their applicability to higher concentra- tions requires proper accounting of prominent solution

tions, especially beyond about 10 molal. This often results in chemistries}hydration and partial dissociation}in addition

poor extrapolation to concentrated electrolyte systems, to energetic interactions among the species ŽRobinson and

multi-electrolyte systems, or mixed-solvent electrolyte sys- Stokes, 1959; Conway, 1983.. For example, cations of transi-

tems. tion elements such as chromium and cobalt exhibit a marked

The electrolyte NRTL model is capable of quantitative- tendency to form hydrated ions. These ions carry with them

ly accurate correlation over the entire concentration range water molecules sufficiently permanently bound to be re-

for many electrolytes, through combination of the Pitzer- garded as part of the ion ŽRobinson and Stokes, 1959.. As for

¨

Debye-Huckel model for long-range ion]ion electrostatic in- partial dissociation, strong acids like hydrogen chloride go

teractions with the NRTL theory for short-range energetic through a smooth transition from effectively complete disso-

ciation at low electrolyte concentrations, to partial dissocia-

tion at medium electrolyte concentrations, to insignificant

Correspondence concerning this article should be addressed to C.-C. Chen. dissociation at high electrolyte concentrations where the acids

1576 July 1999 Vol. 45, No. 7 AIChE Journal

electrolyte concentrations. n is the total hydration number for the electrolyte Žthat is. son ions do not penetrate semipermeable membranes is that water molecules strongly cluster around the ions. Austgen et al. trolyte solutions that we clearly identify the kinetic entity that dence time Žthat is. Similarly. we propose that the ing models for electrolyte solutions. and the To illustrate the general effect of the hydration of ions in solid line represents results with ns 6. the hydrate water associated with Mgq2 relates temperature effects accurately with parameters that has a relatively long lifetime. The original NRTL model cor- diffraction of solids.... apparent molality of the elec- rameters of the electrolyte NRTL model were regressed to trolyte in solution. They also cited independent experimental sociation. Paritosh and Murad Ž1996. 1982. In this work. the dotted line represents results with ns 3.. who considered aqueous sys. an aqueous environment. Robinson and Stokes further developed the underlying relation between the mean molal stoichiometric activity coefficient Žg ". A particularly insightful study is that of the species. in the solution. the NRTL model is used to compute the rational activity co- efficients of water and the ion pairs in the hydrated solution for which the total hydration number is known.: X n n yn ln g "s ln f " y ž ln a w yln 1q / . Figure 1. and local interaction pen Technology. Conway. increasing Hydration Chemistry their size considerably. Chen et al. 1948. we call an ion. drated rather than the nonhydrated ions. ns 0.. Conway et al. and SO4y2 ions. sky and Gruber demonstrated that the combination of hydra. ‘‘hydrated ion’’... it is of utmost bility of small ions such as Liq is that their effective size is importance to our understanding and description of elec- increased due to a cage of water molecules with a long resi. from neutron The focus of this article is on aqueous single electrolyte diffraction and proton NMR studies of solutions and X-ray systems at room temperature.. Ž1998. n represents the summation of stoichiometric numbers of the cation and the anion in the electrolyte. are relatively independent of temperature ŽChen et al. the result of failure to recognize the solution chemistries and taneous account of the solution chemistries and the physical the true species that exist in solutions. 45. As stated by Robinson and Stokes Ž1959. As. electrolyte NRTL model. Chen trolytes with hydrated ions. obtain best fit to the g " data. respectively. In addition. 7 1577 . correlation with strong theoretical and analytical support.. have model. 1979. should be based on concentrations of the hy- of Pinsky and Gruber Ž1992. For example. It can be considered as a bare ion or as a In this work we demonstrate a thermodynamically con. mean ionic activity coefficient in the molality scale. when tems containing Naq. n S In Eq. ŽStokes and Robinson. They some electrolytes only partially dissociate into ions at high reported successful representation of MgCl 2 data by assum. 1. In parameter optimization. the pa- electrolyte vs. the choice profoundly affects the predicted solu- tion behavior. single entity of an ion bound to a certain number of water sistent way to accurately represent the solution nonideality of molecules. 1989. AIChE Journal July 1999 Vol. ing the long range ion]ion interaction. should be considered. have shown that the low mo. 1991. Figure 1 presents values of g " vs. 1998. On the other hand. with x w being the true mole fraction of water in the solution. theoretical considerations regard- and Evans. and thus preventing them from per- meating. Mean ionic activity coefficient of a generic 1-1 1 is used to obtain g ". Pin. posed to apparent ion concentrations based on complete dis- ters of hydration. 1978. 6q2 .. taken as anhydrous. evidence for the hydrated ion ŽMgŽH 2 O. 1986. also see the Appendix.. nq and ny. perceived discrepancies of the NRTL model for highly non- Indeed. is the rational activity of the solvent Žhere water. 1986. Specifically. and they unifying the solution chemistries just mentioned with the should be properly accounted for in first-principle engineer. Ž1. Mgq2 . 1983. No. Koneshan et al. Solution chemistries are aqueous electrolytes over the entire concentration range by inherent parts of electrolyte solution nonideality. phase behavior of many highly nonideal electrolyte ideal electrolyte systems at high electrolyte concentrations are solutions has been satisfactorily described through the simul. pressibility effect is not accounted for in the NRTL model. measured in microseconds. The dashed line represents results with hydration number. for elec- interactions ŽCruz and Renon. the NRTL model has been shown to be an effec- tion with the NRTL model results in a successful engineering tive model for mixed electrolyte systems ŽChen and Evans. Cly. Chen. a w Ž s f wX x w .. and the corresponding ‘‘rational’’ or true mole-fraction-based activity coefficient in a hydrated solution X Ž f" . sum of solvation numbers of cation and anion.exist mainly as molecular species. and then Eq. true ion concentrations Žas op- ing a single thermodynamic entity of Mgq2 ion with six wa. 1987.. we should note that solution com- shown through molecular-dynamics simulations that the rea. 1981. and S is the number of moles of solvent per mole of electrolyte. Kq. These highly advantageous characteristics of the NRTL Other related areas of research have identified the need to model remain as we couple the solution chemistries with the include the hydration of ions.

36 } 5 KH Succinate 0 8.5 NaBr 3 7.7422 0.0233 0.2457 y4.5631 y4.3935 y3.84 1. that result in ically.c a tc a . tm.1624 0.8987 0.19 6 HI 3 7.4520 y3.0481 0.964 y4. trolytes.1193 1.88 6 LiClO4 3 7.40 1.36 4 NaBrO 3 3 7.6303 0. The trolyte solution.95 6 LiCl 3 8. indicating increased ‘‘effective’’ nonideality of the elec.9275 y4.30 0.4468 0.5 KH 2 PO4 0 8.1113 y4.5487 y3.8046 y4.22 4 LiBr 3 8.16 0.7961 y4.4 HBr 3 8.52 } 6 CsI 0 8.9766 0. for elec- ter.0001 y3. Table Continued gexp UU 1 Second number in parenthesis indicates contribution to hydration from OH y.2735 2.68 0. 7 AIChE Journal .6153 y3. we fit- respectively. the ted the binary interaction parameters of the NRTL model predicted g " at higher concentrations also increases dramat.37 0.36 5 Na Propionate 3 5. As the total hydration number increases.72 0.4958 y3.57 3.03 0.9873 y4.5 NaClO4 3 6.1415 y3.1667 0.3977 1.. are set to typical values of 8 and y4.24 } 0. 7.75 3 HCl 3 8.7147 y3.3516 0.9348 y2.97 4.80 3 KAc 0 8.4176 y3. For each hydration number from zero to six.m .52 } 5 CsCl 0 8.01 3 NaH Succinate 3 7.5 KBrO 3 0 7.76 0.2506 y3.2763 y3.5 NaH Malonate 3 6. 1578 July 1999 Vol. 1986.7578 0.13 } 5 KF 0 8.00 0. NRTL nonrandomness factor was set to 0.1304 y3.4926 y3.5 UU KOH 3 Ž0q3.7 KCNS 0 7. for a ‘‘generic’’ 1-1 electrolyte tion we used g " vs.5 KCl 0 8.2105 0.14 } 0.62 3 HNO3 3 5. in data reduc- model ŽChen and Evans.21 } 4.4352 0.14 0.6055 0.1130 0.48 6 LiAc 3 6.5001 0.1636 y2.32 4 LiI 3 6.35 5 NaTol 3 4.08 0. between electrolyte and water.2654 0.0 4 LiTol 3 6.8851 y3.58 } 3. computed by the NRTL With the trend shown in Figure 1 in mind.47 } 3.2 in all calcula- Table 1.99 4 NaI 3 6.1902 0.6067 y4.0359 1.5 NaCl 3 7.4033 0.2984 2.23 } 4.53 6 HClO4 3 8.5735 1. 45. apparent molality Žup to 6 molal.0085 y1.02 1 Na Formate 3 6.12 } 1 KH Malonate 0 7.34 0.4688 0. No.2751 2.2177 0.5116 y3.5 NaAc 3 5.8072 y3.79 3.6636 0.66 0.3557 y4.5 KNO 3 0 7.6555 y3.14 0.1202 y4.2351 y4. data where the model parameters between the electrolyte and wa.36 } 4 KH Adipate 0 5.0004 0.8 KI 0 7.5019 0.0549 y4.7213 0.44 6 NaClO 3 3 5.5851 1.5 CsBr 0 8.3964 0. 7.5 NaNO3 3 6.3317 y4.55 0.5170 y2.12 0.49 1.9111 1.89 3.1700 1.2836 0. the minimum sum of squares error in calculated g ".ca and tca.35 6 UU LiOH 6 Ž3q3.5100 y4.7324 y4.m AADnonhydrated AAD hydrated m 1-1 Electrolytes AgNO3 0 7.9743 y3.79 } 3.8351 0.5304 y4.6601 1.79 0. tm.3872 y3.2220 y3.0989 y3.6465 y3.0748 y3.66 0.6007 y4.30 3. Percent Average Absolute Deviations AAD%U in Mean Ionic Activity Coefficient Calculations Total Hydration % % Max.71 3.33 6 U n < gexp y gcal < AAD%s Ý =100 ns number of data points.4507 1.86 1.64 0. Electrolyte Number tm .78 3 LiNO 3 3 6.0001 y3.77 } 6 CsAc 0 8.5617 1.37 0.1083 0.46 6 NaCNS 3 5.24 } 1.82 1.5 KTol 0 7.0709 0.10 0.22 } 1.99 0.0333 y3.0011 0.m .4980 3.52 } 3 CsNO 3 0 8.38 } 4.1880 0.1480 0.62 0. at 258C presented by Robinson and Stokes Ž1959.22 4 NaF 3 7.0679 y4.apparent molality Žup to 6 molal.ca and tca.5 KClO 3 0 7.0924 0.10 2.66 } 3.02 0.

0000 y4.2031 14. we then selected an absolute deviations Ž%AAD.0960 2.33 1.7292 y2.45 2.4986 3.22 } 0.m AADnonhydrated AAD hydrated m 1-1 Electrolytes UU NaOH 6 Ž3q3. creased average error for MgAc 2 .7302 y3.66 1.16 } 5 RbCl 0 8.0062 0. 6.0797 y4. Studying the results of this data fit. tions.5271 0.3703 1. 1.6736 1.7383 y4.91 2.1300 0.6178 y3.8 2-1 Electrolytes BaBr 2 3 7.11 3.3352 y3. electrolyte containing that ion.6186 y4.92 } 6 TlNO 3 0 9.64 2 MgAc 2 6 6.22 5 BaI 2 3 7.39 5 CuŽNO 3 . Žanion plus cation.63 2 BaCl 2 3 5.7096 y3.07 0.8 K 2 CrO4 0 7. which we consider statisti- nomenological considerations based on ionic radius and cally insignificant. 2 3 7.1392 y4.1109 y3.1153 0.66 1.94 4 CoI 2 6 8.9734 7.3108 1. This is reflected by low water are given in Table 1.96 2.4970 y3.08 5.88 5 U n < gexp y gcal < AAD%s Ý =100 ns number of data points.6412 0.83 6 CoŽNO 3 .95 3.0163 y4.63 6 NH 4 Cl 0 7. For example.23 4 Na 2 SO4 6 Ž3=2..02 2 BaŽNO 3 . 45.37 } 3.0639 0.1983 y3.8446 y4.2050 y4.5255 0.6597 y4.96 3. Electrolyte Number tm .93 } 6 RbAc 0 8.9991 y4.11 2.89 2.93 1. 2 3 8.5347 22.08 4 MgBr2 6 8.4591 0.4239 1. 6.5 TlAc 0 7. The use of hydration slightly increases the average abso- son equation ŽEq.18 } 5 RbNO3 0 7.8986 y4.5 ŽNH 4 .4 CaBr2 6 8.55 } 0.06 0.06 } 6 NH 4 NO 3 0 7.65 5 MgŽNO 3 ..9465 y3. applicable to any tion and that with ‘‘optimum’’ hydration.9734 y3.2453 0. (Continued) Percent Average Absolute Deviations AAD%U in Mean Ionic Activity Coefficient Calculations Total Hydration % % Max.70 } 3.45 5 CoCl 2 6 7. 2 6 6.2872 4. We should note case of Mgq2 .3834 9. 2 6 7.6377 14. Table Continued gexp UU 1 Second number in parenthesis indicates contribution to hydration from OH y.8 BaŽClO4 . 2 6 8.67 6 CaI 2 6 7. 5.92 } 4 Rb 2 SO4 0 7.28 2.8202 0. in g " for the case of no hydra- optimum hydration number for each ion.3153 y4.26 4 Na 2 S 2 O 3 6 Ž3=2.3576 y3. 2 .5178 17.72 1. The selected hydration numbers and corresponding For many of the electrolytes the NRTL model performs NRTL binary interaction parameters between electrolytes and very well without any hydration.16 0. No.0642 8.0649 y3.98 1.62 6 FeCl 2 6 6.c a tc a .00 3.81 3 Na 2 CrO4 6 Ž3=2.47 } 1.3786 y4.6701 0.0252 y3. OHy being the only hydrating anion.8600 2.84 6 CoBr2 6 8.8775 1. Table 1. thus for a given electrolyte the selection This is because a single. 6.9485 y3.1802 y3. The choice of the opti.89 3. accounts for the total hydration number lute deviation for a small number of electrolytes in Table 1. in the factors that we discuss below in more detail.7700 0. 2 6 7. 2 SO4 0 7. 7. charge.06 6 CaŽClO4 . Note that the Stokes-Robin.9677 y3.2106 y3. 2 6 6.9073 y4.5 1-2 Electrolytes Cs 2 SO4 0 7.16 5 MgCl 2 6 8. 7 1579 .8271 y3.85 } 4.9239 1.6248 14. We also report percent average %AAD numbers for many electrolytes with a hydration num- AIChE Journal July 1999 Vol.88 0.43 0.2406 y4.8492 0. considering hydration chemistry with a hydra- that in general we considered only cations as hydrating.7799 7. optimum hydration number is used of hydration number for individual ions depends on other for all electrolytes of a particular cation.4778 y4.46 2 CaŽNO 3 .27 1.2804 3. MgCl 2 and MgŽNO 3 .9460 y4.1485 0.47 } 1.5 RbBr 0 8.8492 0.34 2. with tion number of 6 improves the results significantly for MgBr2 .72 6 CaCl 2 6 7.78 5.5 Li 2 SO4 6 Ž3=2.4410 y4.9304 3.51 4.3147 1.4169 2.4386 12.15 } 5 RbI 0 8.07 0.7515 y3. whereas it results in a slightly in- mum hydration number was further influenced by phe.4 TlClO4 0 9.8613 y3.0000 y3.

represented very well..9816 y4.8324 y3.3612 4. 2 6 9.50 3.46 1.7792 y3.5 3-1 Electrolytes AlCl 3 6 8.9052 y4.4941 2. This electrolyte is specific phenomenon.3234 y4.07 2 U n < gexp y gcal < AAD%s Ý =100 ns number of data points.2443 1.95 2.12 4.2842 y4. were obtained by invoking hydration. and zinc. Ž1982.. magne.45 3.1172 y3.11 1.0849 0.3885 5.45 3 UO 2 ŽClO4 . Figure 3 presents re. Goldberg.54 4 ZnŽNO 3 .5774 y4.26 2. Figure 2 shows the predictions the NRTL model without hydration Žcompare Table 1 with of the NRTL model for three electrolytes without hydration: the analogous table reported by Chen et al.16 7.83 4 MgSO4 6 8.99 1. and consequently weaker in interaction energetics. cobalt. independent of the other ions in solu- only soluble in water up to about 5 molal at 258C.2 CrŽNO 3 .28 3.2292 11.9752 3.0811 y3. Our better predictability of the model parameters.m AADnonhydrated AAD hydrated m 2-1 Electrolytes MnCl 2 6 5.20 2.9023 y3. Hydration Numbers sults for MgCl 2 .15 1.3046 y3.4 ZnSO4 6 8.50 4 NiSO4 6 8.97 2 CrCl 3 3 7.4 EuCl 3 6 7. calcium. consistent with the physical argument of the NRTL interac- ters obtained from fitting data only up to 6 molal.54 1.70 7. gexp UU 1 Second number in parenthesis indicates contribution to hydration from OHy. 2 6 7. only marginal improvements. and at tion.0844 y3.4266 y4.2656 y4.82 2 ScCl 3 6 8.00 4 UO 2 Cl 2 6 5.72 3.7629 y4.85 3. become larger in size For electrolytes containing ions such as lithium.97 2 YCl 3 6 8.73 4 SrŽClO4 .18 2 LaCl 3 6 7.21 4.9988 y4.3775 2.2097 y3. Using the interaction parame.3288 4.9602 10. 1981.7016 0.0743 1. not only gives an excellent fit to the mean ionic activity coef. NH 4 NO 3 . For these systems. is typically 1]2% and essentially always within 5]10%.91 3.5 CdSO4 6 8.3553 2.2208 2.69 2.76 3.0434 6.6811 y4.8298 2. 2 6 9.6940 y2.5 CuSO4 6 8.57 2 SrŽNO 3 .73 2.80 2.8 CeCl 3 6 7.c a tc a .31 6 ZnŽClO4 .35 2 SrCl 2 6 7.24 2.32 1.45 2 SrBr 2 6 6. suggesting the ‘‘smoothed’’ literature data used in data reduction. the entire concentration range up to saturation can be improves the description of mean ionic activity coefficients 1580 July 1999 Vol.76 6 SrI 2 6 6.5 ZnCl 2 6 5. 2 6 7.0646 5.85 5 PbŽClO4 . This is CsCl.62 3.87 2 PrCl 3 6 7.9792 y4.88 1. ber of zero.1179 8. The results in Table 1 suggest that hydration is an ion- progressively better results are obtained. maintaining the same charge number. the improvement due to as.49 1.74 4. Pinsky and Gruber Ž1992.1858 30. ues of the interaction parameters also fall in a narrower band suming hydration is substantial and beyond the uncertainty of than previously reported by Chen et al. 1982.0737 1.4679 4.4929 5.8000 y4. have previ- if any. No. The consideration of hydration chemistry significantly ns6.33 1.03 2.5 MnSO4 6 8.8644 11.2950 4.8884 y4.95 6 PbŽNO 3 . 2 6 8.96 2 NdCl 3 6 7. (Continued) Percent Average Absolute Deviations AAD%U in Mean Ionic Activity Coefficient Calculations Total Hydration % % Max. the model tion parameters and the rationale that hydrated ions. Electrolyte Number tm . The val- sium.64 4.3258 4.0795 y4.52 1.96 1.2066 y4.0324 y4.9935 10. The absolute values of the interaction parameters for the ficient data up to 6 molal but also gives accurate predictions NRTL model with hydration are always smaller than those of far beyond that concentration. 2 6 7. while gives excellent extrapolations up to 20 molal.81 3.00 2.01 2. analysis indicates that uncertainty of the ‘‘smoothed’’ activity coefficients Žfor example.86 1.26 5.9882 2.57 1. 7 AIChE Journal .6769 y4.3737 4. As we consider larger hydration numbers.9272 y3.90 2..1622 2.3447 y4.94 3..69 1.94 6 2-2 Electrolytes BeSO4 3 8. 2 6 5. 3 3 7. and AgNO3.7092 y4.8 SmCl 3 6 7.9049 1.90 6 NiCl 2 6 7.0963 y4. Table 1.6994 y5.7328 5. 45. The NRTL model ously reported similar success for MgCl 2 .9311 1.8219 y3.

The pattern of hydration number Note that there is evidence in independent investigations that vs. The combination of the NRTL model with hydration chemistry not only gives an excellent fit to the mean ionic Figure 3. cations do not ‘‘leak’’ through membranes. The simple pattern of hy- dration number with charge and size suggests a potential pre- dictive method. In addition. No.. they are broadly supported by empirical and theoretical observations. The remain- lal. while anions sometimes do. have reported in computer simu. Cly. of the ion.96 A. but is too small to model parameters were obtained by fitting data up to 6 mo. and Rbq. For example. The havior of the NRTL model for electrolytes with hydration. accommodate more than three water molecules. A larger positive ionic charge increases the hydration number. The 3q metal cations we have stud- ied indicate a pattern that the large ions have a hydration number of 6. Fy.81 A. its small radius. the dashed line represents results with ns 3. tion number of zero. der of the 2A ions follows the trend that larger ions have fewer waters of hydration. Hq. The solid lines represent results computed by the model. Koneshan et al. Ž1998. are zero: they are too large}in addition to the weaker intrinsic tendency of anions to hold water. we dotted line represents results with hydration number. for the 2A group of elements. there may not be any 3q metal cations large enough to show a drop in hydration number. 7 1581 . illustrates these trends. Figure 4. ns 0. Bry. such as Kq. Mgq2 . and a methodology to estimate the hydration numbers of other ions. Mean ionic activity coefficient of MgCl 2 vs. Finally. activity coefficient data up to 6 molal but also gives accurate apparent molality of electrolyte in solution.. which has mapped the hydration numbers onto the periodic table. Mean ionic activity coefficient of electrolytes of 3. and the solid report the results of mean ionic activity coefficient calcula- line represents results with ns 6. charge and Pauling radius of ions Žsee Table 2. These radii are all larger than the values at which the 1q cations begin to have hydration numbers of zero. apparent molality of 6. Csq. While our specific assumptions concerning hydration are clearly an ap- proximation. compound ions will generally have a hydration number of zero. Figure 5 further illustrates the trends presented in the pe- istry is primarily associated with cations appears justified. Our analysis of the hydration numbers for elemental cations in Table 1 suggests a relatively simple correlation in terms of the charge and the radius ŽPauling radius. pattern of the 1A ions. ˚ respectively. Beq2 has a hydration number Figure 2. The explanation is that a small 2q ion The points are data from Robinson and Stokes Ž1959. The results in Figure 5 may also explain why the hydration numbers of the 7A group ions Žhalogen anions. while the small ions have a hydration number of 3. AIChE Journal July 1999 Vol. and Raq2 has a hydra- electrolyte in solution. predictions beyond 6 molal. while the larger ions have a hydration number of zero. ˚ and 2. For the 1A group of elements. Agq Ž1. The like Beq2 has a strong coulombic force.36 A. The 2q transition-metal ions also follow the same simple pattern. Baq2 has a hydration number of 3. Similarly. Liq. tions for LiCl and HCl in Figures 6a and 6b. have shown that the residence time of the water molecules associated with small cations like Liq is significantly longer than the residence times of the water molecules associated with small anions like Fy. and Srq2 each have hydration numbers of requiring no hydration vs. is simple cations are more likely to hydrate than anions.16 A. All the 3q elemental cations for electrolytes with some smaller cations such as Hq and we considered in this work have a hydration number of 6. ˚ 1. For example. the notion that hydration chem.. which has a hydration number of 3. The benefits of inclusion of hydration chemistry dimin. in- creased ionic size decreases the hydration number. due to ish for electrolytes with cations of larger size. lations of reverse osmosis that Žhydrated . Liq. and clear. Caq2 . 45. The trends presented in Figures 4 and 5 provide phe- nomenological supports for our hydration chemistry model. radii of 1.26 A ˚ . To examine the extrapolation be- The points are data from Robinson and Stokes Ž1959. respectively. and Iy have Pauling ˚ 1. the trends in Figure 5 suggest that Žlarge. except for Crq3. riodic table Žsee Figure 4. falls in line with the Paritosh and Murad Ž1996. and Naq each have a hydration number of 3.

Figure 4. The model was found to give sociation mechanism. the model was very success. displaying a much electrolytes in the solution. This is because the hydration true mole-fraction-based activity coefficient in a hydrated so- X ion consumes most of the water present in the system. ing.. no free water would exist if hydration were to re. The NRTL model with hydration predicts positive de- viations.: main the only chemistry in the solution. qj nored for many electrolytes. first the relation between the mean molal stoichiometric tion case. 1y j 1y j 1978. 7 AIChE Journal . at high concentra. Above lution Ž f " . For example. and the corresponding ‘‘rational’’ or begin to deviate from the data. that can be explained by the partial dis- fully fit to data up to 6 molal. Above 10 molal. No. partial dissociation cannot be ig. Žsee the Appendix for details . X n nq nq ny ny ln g " s j ln f " y ln a w y ln ž / y ln ž / n n n qS n n qS Partial Dissociation nq jnq ny jny At high concentrations. the hydration model predictions activity coefficient Žg " . Partial dissociation yields ‘‘molecular’’ very good extrapolation up to 10 molal. 1 needs to be modified as follows 18 molal. as observed in the cases of LiCl g " and HCl g " q n ž ln Sy nq jn q1y j qln f i . 1582 July 1999 Vol. / Ž2. With a hydration number of 3. Hydration numbers and charges of ions mapped on to the Periodic Table. ž n ln Sy nq jn q1y j q n ln Sy nq jn q1y j / tions HCl is only partially dissociating ŽCruz and Renon. given in Eq. 45. To account for this fact in model- improved extrapolation capability compared to the nonhydra. ŽFigures 6a and 6b.

(a) Mean ionic activity coefficient of strong Cesium Cs 1 1.96 0 Iodine I y1 2.Figure 5. Table 2.33 0 Rubidium Rb 1 1.31 3 efficient of strong electrolyte HCl vs. and f i is the rational activity co- Scandium Sc 3 0.72 6 The points are data from Robinson and Stokes Ž1959.76 0 trolyte in solution. with ns 3. the presence of molecular electrolytes in solu- Neodymium Nd 3 1.68 3 Sodium Na 1 0. Nickel Ni 2 0.72 6 dotted line represents results with hydration number ns 0.80 6 given in Table 3.65 6 molality of electrolyte in solution.81 6 Yttrium Y 3 0..99 6 Strontium Sr 2 1. (b) mean ionic activity co- Beryllium Be 2 0.96 6 In addition. 2. apparent Magnesium Mg 2 0.26 0 Potassium K 1 1.81 0 Bromine Br y1 1. j is the fraction of electrolyte dissociated per Barium Ba 2 1.20 6 In Eq.76 6 tial dissociation. respectively.74 6 and the solid line represents results with hydration and par- Iron Fe 2 0.00 6 tion results in additional pairs of interacting species for which Praseodymium Pr 3 1. electrolyte concentrations for hydrating electrolytes such as AIChE Journal July 1999 Vol. Zinc Zn 2 0. with ns 3.48 0 Figure 6.13 6 Lead Pb 2 1. The Copper Cu 2 0. Pauling Radius for Various Ions Total Hydration Name Symbol Charge ˚ R. 45. Anticipat- Cesium Ce 3 1.64 3 the electrolyte.35 3 mole of electrolyte added to S moles of solvent.03 6 ing that there is little free water left in the solution at high Source: Dean Ž1985 . apparent molality of elec- Francium Fr 1 1.97 6 Calcium Ca 2 0.36 0 Chlorine Cl y1 1.95 6 NRTL model. A Number Fluorine F y1 1.69 0 electrolyte LiCl vs. Samarium Sm 3 0. Cobalt Co 2 0.95 3 Silver Ag 1 1. The model parameters are as Manganese Mn 2 0.. Hydration numbers of elemental. metal cations as a function of charge number and size. computed from the Europium Eu 3 0.01 3 Lithium Li 1 0.40 0 are the stoichiometric numbers of the cation and the anion in Chromium Cr 3 0. No. nq and ny Radium Ra 2 1. Cadmium Cd 2 0.16 0 Hydrogen H 1 0.93 6 efficient of the ‘‘molecular’’ electrolyte.74 6 the dashed line represents results with hydration.01 6 the NRTL model parameters must be considered. 7 1583 .

molality data show unusual trends. since the electrolytes are weakly Data are as reported by Robinson and Stokes Ž1959 . for which with the equilibrium constant of the electrolyte dissociation it was not possible to capture the correct trend in the data reaction. The solid lines represent results obtained considering both hy- dissociating. 2 . the triangles are experimental data from Haase et al. CdBr2 . dicted by the NRTL model (solid lines. 1584 July 1999 Vol. there may be sufficient free water and molecular dration and partial dissociation chemistries. with results displayed in Figure 7. and CdŽNO 3 . and thus the NRTL model gives statistically significantly improved results for both the absolute values and the general trend of the mean ionic activity coefficient over the Pitzer model and the Meissner model. reported in Table 3. we assumed that accounting for only the electrolyte] rameters for this pair to zero.Figure 7. Two examples are shown in Figure 9 for Na-caproate and ZnBr2 . Mean ionic activity coefficient of HCl as pre- liquid and in vapor for HClHwater binary mix. Ž1963 . CdI 2 . As we have noted before. apparent mole fraction of HCl in Figure 8. with high accuracy over the entire concentration range.. These the systems we investigated. molecular HCl parameters in addition to the electrolyte] The NRTL model was successfully applied to essentially all water parameters reported in Table 1 would suffice. we also considered the vapor]liquid equilibrium ŽVLE. at 258C of HClqwater mixture. the model is Na-caproate and ZnBr 2 vs. apparent molality capable of accurately describing the inflections observed in of electrolyte in solution. For these cases. hydration and partial dissociation chemistries. The only exception is cadmium additional NRTL model parameters were regressed together electrolytes ŽCdCl 2 . With the NRTL model parameters and the dissociation constant Ž K diss . Mean ionic activity coefficient of electrolytes for electrolyte dissociation reported in Table 3.. with ture. and without hydration and partial dissociation The dots are experimental data from Vega and Vera Ž1976. chemistries). The results of such a parameter-fitting exercise are shown in Figures 6a and 6b for LiCl and HCl for g ". The model can also be used to correlate mean ionic activ- ity coefficients of some relatively weaker electrolytes for which the g " vs. These results show that accounting for the par- tial dissociation at high concentrations enables the NRTL model to correlate and extrapolate the mean ionic activity coefficients Žand VLE in the case of HCl. with parame- ters given in Table 3. with parameters electrolyte in the solution so that the binary interactions be. 45. the solid lines represent results calculated considering both and the Meissner model (dashed line). the data. the uncertainty in the smoothed experimental data is less than 10%. Figure 9. Pressure vs. 7 AIChE Journal . For the HCl case. Ž1986.. we have arbitrarily assumed that we can set the binary interaction pa- HCl. No. Figure 8 further shows the improved results of the NRTL model for the mean ionic activity coefficient of HCl in com- parison with those of the Pitzer model and the Meissner model as reported by Zemaitis et al... tween this pair need to be accounted for. However. the Pitzer model (dotted line).

such as complex formation.7374 y10.72 Ž16. Res.. and C.5852 1. V.1107 y3. Peng. Rochelle.-C.c a tc a .2751 } } } 10..2984 0.. ŽMax. at low to moderate electrolyte concentrations but also pro- tween water and ion pairs. Britt. C..26 Ž4. C. apparent molality of electrolyte in solution. 25. Chen.. Chen. Chen. Na-caproate 3 8. D.m tm . Parameters Used in Various Modeling Modes and Model Performances Water]Ion Pair Electrolyte]Ion Pair Hydration Parameters Parameters ln % AAD Electrolyte No. 313 Ž1973. 30. ‘‘Some Recent Developments in Process Simulation for Reactive Chemical Systems. Cambridge. 588 Ž1982.1121 y1. electrolytes. Representation of H 2 S and CO 2 Solubility in Aqueous MDEA and CO 2 Solubility in Aqueous Mixtures of MDEA with MEA or DEA. HCl 3 8. as the true species in the solution. ‘‘Extension and Application of the Pitzer Equation for Vapor-Liquid Equilib- rium of Aqueous Electrolyte Systems with Molecular Species. T. All model parameters are given in Table 3.’’ Ind. Watanasiri. 1177 Ž1987.. 150 Ž1998. B.0549 y4.76 Ž16.. Figure 10.2117 } } } 14. trations of 6 molal or less.61 Ž20. This should be further hydrated ions and molecular electrolytes considered explicitly investigated in the future. X. tm . For electrolytes that exhibit hydra- ported in Table 3. Liu.0549 y4. E. H. Chen. Hydration and Partial Dissociation LiCl 3 8.-C. H...22 0. I. J. Conway. ‘‘Ionic Interactions and Activity Behavior of Elec- ation. Austgen. ‘‘Model of Vapor- Liquid Equilibria for Aqueous Acid Gas]Alkanolamine Systems..’’ hydration and partial dissociation chemistries. In Figure 10 the results for CdCl 2 vides excellent extrapolation capability into the high-con- are shown. CdCl 2 6 13. Bromley.. Rochelle. lines represent results with no hydration or partial dissoci. J. with acceptable values for binary interaction parameters be..3524 y0.. ‘‘Representation of Non- Ideality in Concentrated Electrolytes Solutions Using the Elec- trolyte NRTL Model with Concentration-Dependent Parameters.60 Ž6.1932 y19.0671 5. A. ‘‘Local Com- The solid line represents results obtained considering both position Model for Excess Gibbs Energy of Electrolyte Systems. Inc. ZnBr2 6 7. Aspen Plus Steady State Simulation. Eng. Austgen.91 1. The use of hydration and partial dissociation chemistries with the electrolyte NRTL model provides a comprehensive thermodynamic framework Conclusions with strong correlative and extrapolative capability in repre- The electrolyte NRTL model has been shown to success.. Chem.-C. T. For electrolytes that show no hydration.45 1. 45. Version 10 Reference Manual.’’ Pure Appl. D.93 1. and L. Evans. Evans. Britt. 820 Ž1979.6085 3. are chemistries should be taken into account properly and the playing a role for these electrolytes. 28. Vol. AIChE Journal July 1999 Vol. Mean ionic activity coefficient of CdCl 2 vs. An accurate fit of the data was possible only with centration region. senting aqueous electrolyte nonideality over the entire con- fully represent the solution nonideality for many aqueous centration range. Chem.030 y5. with the parameters obtained at concen- the exceptionally large binary interaction parameters re. Y..424 y6... B. M.4970 y2.2984 } } } 9. C. trolyte Solutions.’’ Comprehensi®e Treatise of Electrochemistry.’’ AIChE J. Chen. 2.0140 y4...1202 y4. It is worthwhile exploring to determine tion andror partial dissociation. I. Table 3. Hydration Only LiCl 3 8.5716 y2. No Hydration or Partial Dissociation LiCl 0 10. F. HCl 3 8. 59. the model not only correlates accurately the solution nonideality Literature Cited Abovsky. MA Ž1998. F. 32.’’ AIChE J.089 y5. and L.1537 } } } 25. ‘‘Model of Vapor-Liquid Equilibria for Aqueous Acid Gas]Alkanolamine Systems Using the Electrolyte NRTL Equation. and C. 28.. G.35 Ž20. Evans. L. m. No..’’ AIChE J. Chem.4408 y4. 543 Ž1991. C.1202 y4. and L. B.4751 9. HCl 0 10. The dashed AIChE J.67 1.-C. 7 1585 .. it is essential that such whether other mechanisms. ‘‘A Local Composition Model for the Excess Gibbs Energy of Aqueous Electrolyte Systems..-C.’’ Fluid Phase Equilibria. 1060 Ž1989.27 Ž6.52 Ž16. G.2751 0.5.9411 2.6158 13.-C.m Ž K diss .52 Ž20. Boston. M.c a tc a . Boston. Aspen Technology..’’ Ind.. and S. Eng. B. Res.. 19. ‘‘Thermodynamic Properties of Strong Electrolytes in Aqueous Solutions. Aspen Technology. 444 Ž1986. Chen.

H. Dynamics and Ion Mobility in Aqueous Solu- tions at 258C. 37. ‘‘Thermodynamics of Electrolytes: I. Goldberg.. and rearranging Chem. 90. 42. Robinson. Elsevier. 2 of the text. and R. Electrolyte Solutions.. Loehe. B. H. 1999. ‘‘Ionic Hydration and Activity in Electrolyte Solutions. Y. 4193 Ž1998.. and ous Solutions Containing Volatile Strong Electrolytes. H.. In addi- of water: tion there is Ž1y j . Haghtalab. Conway.’’ AIChE J. Manuscript recei®ed Jan. Vera. Murad. H. A. of Binary Electrolyte Solutions Nonideality in the Whole Range of Concentrations. ‘‘Experimentelle Untersuchun- X X gen uber das Thermodynamische Verhalten Konzentrierter Halo.. A.’’ AIChE Symp. Ionic Hydration in Chemistry and Biophysics. Ž A1. ‘‘Phase Equilibria in Aqueous Systems Containing Naq.1rn X nqX n yX . M. New York Ž1983. and R. Hand. Sci. Data. Des. S™`. and SO4 y2 Ions Using the NRTL It is more practical to relate the rational activity coefficient X Model. Vera. DIPPR. Ref. E. Cly.. nq ny . all logarithmic terms Liu.. Ž A4. Stokes. Mgq2 . 803 q n ln Ž a w . ‘‘Evaluated Activity and Osmotic Coefficients for Aqueous Solutions: Thirty-Six Uni-Bivalent Electrolytes. 102. Gruber. H. Vera. 46. ‘‘Recent Advances in Modeling Considering this.000rŽ MWw = m .1rn cients f "s Ž fq fy and f " s Ž fq fy . S. R. ‘‘A New Thermodynamic Representation tional activity coefficients and mole fractions. p. M.. No. No. X n Sq n y n Paritosh.. 1586 July 1999 Vol. R. D. Bockris. F.’’ AIChE J. 24.. Chem. R. terms on the lefthand side of Eq.’’ Ind.’’ J. Rafal. Clark. present in detail ln g "s ln f " y ln a w yln 1q ž / . Pinsky. Thus. London. A. Haase.. S. and N. 6.-L. 112 Ž1994. and H. Stokes. H.’’ Can... 1: Appendix X n n yn Conway Ž1981. and J. and Conway et al. and J... Yeager. Chem. 2nd ed. q n ln q nq ln fq q ny ln fy Ž1988. 817 Ž1978. K.. ln f " s ln f "q n ln a w qln ž Sq n / . and G. 180 Ž1997. A3 can be tems.. Rasaiah.000 . R. solution properties in a hydrated solution. Phys. and S. 1870 Ž1948. 5. Chem. Scrivner. H.’’ J. Eng. the measured properties must remain the same. Soc. At the limit of infinite dilution. A. ‘‘A Nonrandom Factor Model for the Sq n y n Excess Gibbs Energy of Electrolyte Solutions. Below is a brief summary of this treatment. Chem. De®. Ž A2. C. New York Ž1986. the free energy of the solution. Amer. Butterworths.. Ž1983. 70. R... Thumm. G.. hence. and M. 54... Haghtalab. P. 210 Ž1963. book of Aqueous Electrolyte Thermodynamics: Theory and Applica- tion. contributing to the total Gibbs free energy of the Gs Sm w q nq mq q ny my s Ž Sy n . rRT q ny Ž my0 y my0 . Chem. J.’’ J. considering ion hydration for a solution that moles of water. Donohue. and U. is molality. Phys.’’ Z. 11. ‘‘Activity Coefficients of Strong Electrolytes in Aqueous Solutions. terms of the apparent concentrations. R. Ser. 7 AIChE Journal . AIChE. 245 Ž1976. 671 Ž1981. eds. F. resulting in Eq.. nq Ž mq 0 y mq 0 .. B.. 77.. ed. J. H. the Stokes and Robinson treatment that results in Eq. L. Eq.. moles of molecular electrolyte left in the solution.. O’M.. M. m i s m0i q RT ln a i s m0i q RT ln Ž x i f i . .. McGraw.’’ J. J. Koneshan. Lee. and J. B.. 45. solution. A3 become zero.. and the number of moles of anion is jny. Gren. J. arranged as Meissner. J.. 147 Ž1991. Zemaitis. Vega.. can be written in In writing Eq... 2984 Ž1996. Lange’s Handbook of Chemistry. and E. . ‘‘Molecular Simulations of Osmosis and Reverse Osmosis in Aqueous Electrolyte Solutions. Ss1.. and J. 13th ed. Eng. Ž A3. and m solution. and also introducing mean activity coeffi- Thermodynamic Properties of Aqueous Strong Electrolyte Sys... Proc. cal potential terms with their counterparts in terms of ra- Cruz. substituting the re- Pitzer. J. 1999.. and re®ision recei®ed May 18. Replacing chemi- Amsterdam Ž1981.. or in terms of the true but consider that for each mole of electrolyte added to S concentrations.. Robinson. ‘‘Simultaneous Correlation of Activity Coeffi- cients for 55 Aqueous Electrolytes Using a Model with Ion Spe- in Eq. Naas.. A. Lynden-Bell. W. D. M. Hill. 298. 128 Ž1972. Phys. rRT q n m0wrRT genwasserstoffsauren.’’ AIChE J. m w q nq mXq q ny mXy . Dean.. C. Eng.. Chem... the sum of the first three cific Parameters. Regardless of the model chosen to describe an electrolyte Here MWw represents the molecular weight of water.. Renon. The terms with a prime represent the true Plenum Press. 1815 Ž1991. and H. R. Theoretical Basis lations below in Eq. Tester. s nq ln fq q ny ln fy .’’ AIChE J. E. 43.’’ AIChE J. A4 and General Equations. ‘‘Solvent Structure.. the number of moles of cation in the solution contains nq moles of cation and ny moles of ion in S moles is jn q. ln f "s ln g " Ž 1q n = MWw = mr1.. 10. N. ‘‘Phase Equilibria of Concentrated Aque. we follow the same treatment. 34... New York Ž1985. 37.’’ Chem. 268 Ž1973... 1 of n S this article. hydration number. Conway. f" to mean molal activity coefficient g ". and S. Kq. Thermodynamic and Transport Properties of Aqueous and Molten The m terms represent chemical potentials and n is the total Electrolytes. A3 must also be zero. Jr. Phys. 54 Ž1959. ‘‘Nonrandom Factor Model for Elec- ž Sq n / X X trolyte Solutions. J.

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