J. Chem.

Thermodynamics 1998, 30, 3 12

Partial molar volumes at infinite dilution in aqueous solutions of NaCl, LiCl, NaBr, and CsBr at temperatures from 550 K to 725 K
Josef Sedlbauer,
Department of Chemistry, Technical Uni ersity Liberec, Halko a 6, 461 17 Liberec, Czech Republic

Eric M. Yezdimer, and Robert H. Wood a

Department of Chemistry and Biochemistry and Center for Molecular Engineering Thermodynamics, Uni ersity of Delaware, Newark, DE 19716, U.S.A.

Partial molar volumes at infinite dilution provide a convenient test of theoretical models of aqueous solutions. In this communication, previously published experimental results of the apparent molar volumes for NaCl, NaBr, LiCl, and CsBr at near-critical conditions were extrapolated to infinite dilution. In the temperature range included in this study 550 to 725. K, ionic association processes must be considered. Using recently proposed equilibrium constants for alkali halides included in this study, the extrapolations were corrected for ion-association effects. Partial molar volumes at infinite dilution for free ions and ion pairs are reported for each electrolyte. 1998 Academic Press Limited KEYWORDS: volumes; aqueous; salts; high temperature

1. Introduction
Measurements of the apparent molar volumes in aqueous solutions of several alkali halides at near-critical conditions were performed in the laboratory at the University of Delaware in previous years and the experimental results were published in this Journal.1 3. For many purposes, namely tests of predictions of theoretical models, it is convenient to process these results and calculate the partial molar volumes at infinite dilution. However, at temperatures above T f 550 K, the extrapolations cannot be accurate without consideration of ionassociation reactions which occur in the solutions. Independent conductance measurements are therefore required as a source from which the equilibrium constants of association reactions may be evaluated. Except for NaClaq.,4 7. conductance measurements were not thought to be extensive enough to warrant their use in an extrapolation, until the recent results of Zimmerman et al.8. and Gruszkiewicz and Wood9. were obtained. The latter authors have recently proposed
a

To whom correspondence should be addressed E-mail: RWOOD@udel.edu..

1998 Academic Press Limited

0021 9614 r 98 r 010003 q 10 $25.00 r 0 r ct970262

J. Sedlbauer, E. M. Yezdimer, and R. H. Wood

equations for calculating the equilibrium constants of association reactions for several 1 1 electrolytes. The purpose of this communication is to provide estimates of the partial molar volumes at infinite dilution for four alkali halides. The results for NaCl are also compared with the earlier extrapolations reported by Majer and Wood.3.

2. Results
Association reactions which occur in the solutions of 1 1 electrolytes at high temperatures above T f 550 K. are represented by the following equations: Aq aq . q By aq . s AB aq . , m A . s m B . s m "s 1 y . . m , m AB. s . m ,
q y

1. 2. 3.

where m is stoichiometric molality and is the degree of association of the electrolyte in the solution, which can be calculated from the equation for the equilibrium constant of reaction 1.:
2 2 K s . 0r 1 y . . m . " ..

4.

Because there is no reliable model for the activity coefficient of the ion pairs available, 0 was considered to be equal to unity at all experimental conditions and the mean activity coefficient " was estimated from the extended Debye Huckel formula: 10. ln "s yA . I 1r 2r 1 q 1.2 . I 1r 2 . q 2r1.2. . ln 1 q 1.2 . I 1r 2 . 4 ,

5.

where A is the osmotic slope in the Debye Huckel limiting law, calculated from Archer and Wang,11. and the ionic strength I s 1 y . . mrm 0 ., with m 0 s 1 mol . kgy1 . The empirical correlation proposed by Gruszkiewicz and Wood9. for representation of the equilibrium constant of reaction 1. for alkali halides was used in calculations referred to in this study. The six-parameter formula is given by: ylg K s a1 y 1.2 . 10 3 . T0rT . q a2 . r 0 . q a3 . 0r .
3 q a4 . exp a5 . T y Tc . rT0 4 q a6 . 3r 0 ,

6.

where T0 s 1 K, Tc s 647.15 K, 0 s 1 kg . my3 , is the density of pure water, a3 s 1291.0, a4 s y1.7768, a5 s 0.037829, a6 s y4.417 . 10y8 , and the adjustable parameters a1 and a2 are listed in table 1. The density range used to evaluate these parameters was 650 kg . my3 to 200 kg . my3 for NaClaq. and CsBraq., and 650 kg . my3 to 250 kg . my3 for LiClaq. and NaBraq.. In accordance with the assumptions made for activity coefficients ideal behavior

V20 of NaClaq., LiClaq., NaBraq., and CsBraq. TABLE 1. Parameters of equation 6. for different alkali halides Electrolyte NaClaq. LiClaq. NaBraq. CsBraq. a1 1.5089 1.3889 1.2289 1.1189 10 4 . a2 y4.3583 y1.3583 0.6417 1.6417

of ion pairs and no interaction between ion pairs and free ions., we can express the apparent molar volumes of electrolytes by: Vexp s 1 y . . V Aq . q V By . 4 q . V AB. ,

7.

where the apparent molar volumes of ion pairs are considered to be constant and 0 : equal to partial molar volumes at infinite dilution VAB
0 V AB. s VAB .

8.

The molality dependence of the apparent molar volumes of free ions is represented by a simple form of the Pitzer ion-interaction model:10.
0 V Aq . q V By . s V " q AVr1.2. . ln 1 q 1.2 . IrI 0 .

1r 2

5 q 2 . RT . m

" BV

9.
where AV is the Debye Huckel slope for volume, calculated again from Archer and Wang,11. I 0 s 1 mol . kgy1 , and BV is the ion-interaction parameter. Equations 8. and 9. substituted into equation 7. yield the final formula for extrapolating the experimental results of the apparent molar volumes. A weighted least-squares procedure was used for the calculations with weights equal to 1r 2 , where is the estimated experimental uncertainty presented in the original papers.1 3. Our simple model could not be used for the description of experimental results at higher molalities, where the ionic association is very high, or re-dissociation processes occur, because the interaction between strongly polar ion pairs and free ions are presumably very important under these conditions. We followed Majer and Wood3. and used only experimental results up to the target molality m s 0.5 mol . kgy1 for extrapolations at T - 605 K, and results up to the molality m s 0.1 mol . kgy1 at T ) 605 K. It should be noted that some of the conditions reported by Majer and Wood3. for certain alkali halides do not contain a suitable number of experimental points at least four. or a solid distinguishable trend over the molality range examined to obtain a reliable extrapolation. Therefore, the results for those conditions are not reported in this study. With the limitations of molality range outlined above, all three adjustable 0 0 parameters V " , BV , and VAB , were found to be numerically correlated in some 0 0 cases, and the accuracy of the results of interest V " and VAB might be reduced by

J. Sedlbauer, E. M. Yezdimer, and R. H. Wood

TABLE 2. Comparison of extrapolations for NaClaq. using different equations for ionic association 0 0 0 0 constants, where V 0 s VAB y V" , V" is the infinite dilution volume of free ions, and VAB is the infinite dilution volume of ion pairs T K 548 548 597 604 604 651 665 670 651 669 681 687 691 548 597 604 651 673 691 703 710
a

p MPa 11 25 21 19 27 28 28 28 33 33 33 33 33 37 39 37 38 38 38 38 38

V 0 a cm3 . moly 1 100 88 171 211 165 721 5756 12010 404 1104 3655 5510 6542 81 125 138 299 650 1859 3580 4288
b

V 0 b cm3 . moly 1 40 32 96 133 90 687 5031 9330 344 1094 3327 4754 5571 27 57 68 230 620 1828 3221 3784

0 a V " 3. cm moly 1

0 b V " 3. cm moly 1

y58 y38 y167 y223 y152 y1059 y7713 y16301 y577 y1671 y5076 y7595 y8921 y30 y95 y112 y410 y1015 y2779 y4991 y5865

y53 y37 y156 y217 y148 y1054 y7103 y13467 y567 y1654 y4787 y6848 y7889 y27 y89 y108 y400 y1000 y2732 y4648 y5334

Results from Reference 3.

Results of this study.

this effect. In order to stablize the extrapolation and to allow for the use of a minimum number of adjustable parameters, we used the thermodynamic relation:
0 0 VAB y V" s yRT ln Kr p . T s yRT ln Kr . T r p . T

s yRT ln Kr ln . T T ,

10 .

where T is the coefficient of isothermal compressibility of pure water. Applying this relation, equation 6. yields:
0 0 2 V 0 s VAB y V" s yRT ln 10 . T r 0 . . a2 y a3 . 0 r 2 . q 3 2 3 a4 . exp a5 . T y Tc . rT0 4 q a6 3r 0 a6 2r 0 . . 11. 0 In table 2, the new results for V " and V 0 in NaClaq. solutions are compared with the older calculations of Majer and Wood.3. Agreement between both sets is very good, considering the difficulty of extrapolation, and gives us confidence in our extrapolations. It is surprising that equation 11. yields V 0 LiCl. V 0 NaCl.; the difference is small and probably reflects the difficulty of calculating

V20 of NaClaq., LiClaq., NaBraq., and CsBraq.

TABLE 3. Extraplated partial molar volumes at infinite dilution for NaClaq., LiClaq., NaBraq., and 0 0 0 0 CsBraq.. V 0 s VAB y V" , where V " is the infinite dilution volume of free ions, VAB is the infinite dilution volume of ion pairs, and BV is the ion-interaction parameter in equation 9. T K p MPa V 0 cm mol
3. y1 0 V " 0 VAB y1

cm mol

3.

cm mol

3.

y1

BV . kg MPay 1 . moly 1

NaClaq. 548.05 548.05 597.45 604.41 604.41 651.11 665.39 669.94 673.19 651.11 668.86 681.10 686.55 691.19 696.66 548.05 597.45 604.42 651.11 673.19 691.20 703.12 709.55 716.72 725.50 604.41 604.41 651.10 665.39 669.94 673.19 651.11 668.86 681.11 686.56 691.20 604.42 651.10 673.18 691.19 703.12 709.55 716.72 10.86 24.66 20.65 18.51 27.44 28.00 28.01 28.00 28.00 33.00 33.00 33.00 33.01 33.00 33.00 37.13 38.68 37.41 37.99 38.00 38.01 38.00 38.00 38.01 38.01 18.49 27.48 28.00 28.00 28.00 28.00 33.00 33.00 33.00 33.01 33.00 37.40 38.00 38.00 38.01 38.00 38.00 38.02 40 32 96 133 90 687 5031 9330 10052 344 1094 3327 4754 5571 5990 27 57 68 230 620 1828 3221 3784 4158 4393 121 82 647 4847 9093 9868 321 1039 3216 4633 5461 61 213 585 1758 3140 3708 4087 y53 y37 y156 y217 y148 y1054 y7103 y13467 y14351 y567 y1654 y4787 y6848 y7889 y8305 y27 y89 y108 y400 y1000 y2732 y4648 y5334 y5774 y6075 LiClaq. y226 y158 y1083 y7000 y13204 y13994 y582 y1664 y4713 y6659 y7662 y117 y406 y1034 y2698 y4512 y5177 y5534 y105 y76 y436 y2153 y4111 y4126 y261 y625 y1497 y2026 y2201 y56 y193 y449 y940 y1372 y1469 y1447 3.16 . 10y3 3.01 . 10y3 0.169 3.71 17.9 56.7 5.05 . 10y2 0.311 2.22 7.36 18.8 1.84 . 10y3 3.30 . 10y2 0.257 1.04 4.88 13.5 27.1 y13 y5 y60 y84 y58 y367 y2072 y4137 y4299 y223 y560 y1460 y2094 y2318 y2315 0 y32 y40 y170 y380 y904 y1427 y1550 y1616 y1682 6.93 . 10y4 3.10 . 10y4 1.77 . 10y3 2.53 . 10y3 1.92 . 10y3 0.109 4.01 22.2 99.7 4.16 . 10y2 0.237 2.36 10.2 34.7 1.74 . 10 2 5.97 . 10y5 1.25 . 10y3 1.41 . 10y3 3.77 . 10y2 0.149 1.09 6.80 18.7 1.16 . 10 2 1.20 . 10 3

J. Sedlbauer, E. M. Yezdimer, and R. H. Wood TABLE 3 continued T K p MPa V 0 cm3 . moly 1

0 V " cm3 . moly 1 0 VAB cm3 . moly 1

BV kg . MPay 1 . moly 1

NaBraq. 604.42 604.41 651.11 665.39 669.94 673.19 651.10 668.86 681.11 686.56 691.20 604.42 651.11 673.19 691.21 703.12 709.56 716.71 604.41 604.42 651.10 665.39 669.94 673.19 651.11 668.87 681.11 686.56 691.20 604.43 651.11 673.19 691.21 703.12 709.55 716.72 18.50 27.48 28.01 28.00 28.00 28.00 33.01 32.99 33.00 33.01 33.00 37.49 38.00 38.00 38.00 38.00 38.00 38.00 18.47 27.46 28.01 28.00 27.99 28.00 33.01 32.99 33.00 33.01 33.00 37.46 38.00 38.00 38.00 38.00 38.00 38.00 113 76 618 4714 8922 9756 305 1003 3141 4548 5383 56 202 562 1715 3087 3656 4048 110 73 604 4667 8892 9698 297 985 3101 4511 5344 54 197 550 1692 3060 3630 4026 y204 y134 y1036 y6940 y13304 y14232 y567 y1643 y4702 y6701 y7827 y95 y384 y979 y2686 y4529 y5260 y5703 CsBraq. y172 y103 y1008 y6830 y13749 y14325 y505 y1534 y4657 y6691 y7966 y65 y340 y934 y2665 y4568 y5359 y5853 y62 y30 y404 y2163 y4857 y4627 y208 y549 y1556 y2180 y2622 y11 y143 y384 y973 y1508 y1729 y1827 2.77 . 10y3 1.03 . 10y3 0.134 2.14 14.4 42.4 2.36 . 10y2 6.37 . 10y2 1.40 4.57 20.5 1.23 . 10y3 1.78 . 10y2 0.117 0.719 3.23 11.7 63.3 y91 y58 y418 y2226 y4382 y4476 y262 y640 y1561 y2153 y2444 y39 y182 y417 y971 y1442 y1604 y1655 3.26 . 10y3 1.84 . 10y3 0.112 3.11 15.2 54.7 7.81 . 10y2 0.248 1.77 6.05 20.3 1.28 . 10y3 3.71 . 10y2 0.135 0.803 3.31 11.3 47.2

V 0 from the pressure derivative of ln K . At the highest temperatures at every 0 isobar, the values of V " of Majer and Wood tend to be lower than the new calculations. We repeated the calculations of Majer and Wood and found the same systematic difference between V 0 from their equation for the association constants and V 0 from the equation of Gruszkiewicz and Wood used in this work. It should be noted that the lowest densities used in our extrapolations are

V20 of NaClaq., LiClaq., NaBraq., and CsBraq.

still within the limits of the density range used for adjusting the parameters in equation 6., while this is not true in the case of Majers equation for lg K . The 0 0 complete sets of calculated V " , BV , VAB , and V 0 for all alkali halides are reported in table 3.

3. Discussion
As discussed previously, the present extrapolation method should fail if the measurements are too close to the critical point 12,13. because critical effects become larger than the Debye Huckel limiting law on the critical isotherm and isobar. However, the previous extrapolations of the NaCl results 3. and the present calculations do not yield any evidence for critical point effects. More recently, Gruszkiewicz and Wood9. used a Debye Huckel Bjerrum activity coefficient in treating conductance results near the critical density and at 2.5 K above the critical temperature, and also found no evidence of critical point effects.
3 .

0 FIGURE 1. Plots of parameter D 12 s V " r T RT . against H 2 O. for free ions. a, Naq aq. q Cly aq.; b, Liq aq. q Cly aq.; c, Naq aq. q Bry aq.; d, Csq aq. q Bry aq.. `, p s 38 MPa; I, p s 33 MPa; , p s 28 MPa.

10

J. Sedlbauer, E. M. Yezdimer, and R. H. Wood

There are several sources which contribute to the uncertainties of the extrapolations reported in table 3. Experimental uncertainties in the values of apparent molar volumes are unavoidable and we tried to reduce their effect on the extrapolated values by using the weighted least-squares procedure. Uncertainties in representing the association constants and their pressure derivatives are other sources of error in extrapolations. To estimate the effect of inaccuracies in calculations of the degree of association and V 0 is a difficult task: we can only judge their contributions from the differences between our extrapolations and those of Majer and Wood see table 2., because different equations for ln K were used in both sets of calculations. Disagreement becomes apparent at high temperatures, where it is almost 10 per cent 20 per cent in one case.. Another source of error arises from our assumptions and the method used for extrapolation. In order to summarize all the effects mentioned above and to estimate the

0 FIGURE 2. Plots of parameter D 12 s VAB r T RT . against H 2 O. for ion pairs. a, NaClaq.; b, LiClaq.; c, NaBraq.; d, CsBraq.. `, p s 38 MPa; I, p s 33 MPa; , p s 28 MPa.

V20 of NaClaq., LiClaq., NaBraq., and CsBraq.

11

TABLE 4. Parameters of equation 12. for different alkali halides, free ions and ion pairs. The average relative error of the correlation is given by , and is the maximum relative error 10 2 . a0 y33.206 y8.1361 y26.472 y6.9149 y27.747 y8.1557 y28.721 y9.1988 10 4 . a1 10 7 . a2 NaClaq. Free ions Ion pair Free ions Ion pair Free ions Ion pair Free ions Ion pair 18.274 4.2091 13.656 3.5438 14.405 4.2348 14.962 4.8289 y36.306 y7.9752 LiClaq. y25.956 y6.8524 NaBraq. y27.386 y8.1480 CsBraq. y28.467 y9.3178 18.576 6.1088 4.1 4.9 8.6 13.7 17.784 5.2504 3.7 3.8 10.7 10.8 16.851 4.4183 3.8 4.4 9.9 11.7 24.451 5.0596 4.3 4.6 11.3 12.4 10 10 . a3 10 2 . 10 2 .

accuracy of tabulated results, we made an independent check of our calculations. It has been our experience,3,14,15,18. which has some background in the theory of near-critical phenomena16. that, near the critical point plots, of the functions V 0 y VmH 2 O.4 r T RT . or V 0r T RT . against density, or some function of density, produce smooth curves on which the points at the same densities are very 0 close to each other, regardless of pressure. Plots of D 12 s V " r T RT . and 0 D 12 s VAB r T RT . against , are shown in figures 1 and 2. For T - 605 K, the 0 new extrapolations are in excellent agreement with the V " values of Archer.17. At T ) 605 K, we found that a third-order polynomial in density provided good correlation of D 12 for free ions and also ion pairs of all solutes: D 12 s a0 q a1 . r 0 . q a2 . r 0 . q a3 . r 0 . ,
2 3

12 .

where 0 s 1 kg . my3 . Parameters of equation 12. and calculated average relative errors and maximum relative errors are summarized in table 4. The accuracy of this description of D 12 allows us to estimate the uncertainty of our extrapolations due to random experimental errors and the choice of the method to be about 5 per cent 0 0 of the absolute values of V " and VAB . 0 The values of V " predicted from equation 12. at G 400 kg . my3 follow the 0 order: LiCl f NaCl - NaBr - CsBr, and the values of VAB at F 350 kg . my3 increase in the opposite way: CsBr - NaBr - NaCl - LiCl. Both orders are in agreement with the arguments put forward by Majer and Wood3. about the influence of free ions and ion pairs of different sizes on the properties of solutions. However, at lower densities, the sequence for free ions is changed to: NaCl CsBr - NaBr - LiCl, but the differences are not much larger than our estimated uncertainties. Similarly, the sequence for ion pairs is changed at higher densities to: LiCl - NaBr - CsBr - NaCl. It should be noted that at higher densities the

12

J. Sedlbauer, E. M. Yezdimer, and R. H. Wood

0 uncertainties in evaluating VAB are high, because the ions are only weakly associated 0 under these conditions. Similarly, for V " at lower densities, the uncertainties are higher, because at these conditions and at molalities included in this study, most of the ions are associated. On the other hand, the regularity of these unexpected features suggests that random experimental errors are not responsible for the effect and that some other systematic error might be involved: perhaps, for example, a systematic effect arising from our neglect of ion dipole and dipole dipole interactions in calculating the activity coefficients in equation 4.. 0 We would expect to observe a minimum of V " near the maximum of T ; however, the experimental data do not extend far enough beyond this maximum to enable us to discern the predicted minimum within the uncertainties of our extrapolations. Based on the above findings, we conclude that the extrapolated values of the partial molar volumes at infinite dilution of free ions reported in table 3 are reliable, with uncertainties varying from 5 per cent to 10 per cent as the temperature increases. The absolute values of the partial molar volumes at infinite dilution of ion pairs are lower and, therefore, the relative uncertainties are higher; we estimate them to vary from 7 per cent to 20 per cent as the temperature decreases.

The authors would like to thank John OConnell and Vladimir Majer for their helpful discussions and comments. This work was supported by the Department of Energy DOE. under grant number DEFG02-89ER-14080 and by the National Science Foundation under grant CHE9416564. Such support does not constitute endorsement by the DOE or NSF of the views expressed in this article.
REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. Majer, V.; Hui, L.; Crovetto, R.; Wood, R. H. J . Chem. Thermodynamics 1991, 23, 213 229. Majer, V.; Hui, L.; Crovetto, R.; Wood, R. H. J . Chem. Thermodynamics 1991, 23, 365 378. Majer, V.; Wood, R. H. J . Chem. Thermodynamics 1994, 26, 1143 1166. Fogo, J. K.; Benson, S. W. J . Am. Chem. Soc. 1954, 22, 212 216. Pearson, D.; Copeland, C. S.; Benson, S. W. J . Am. Chem. Soc. 1963, 85, 1047 1049. Quist, A. S.; Marshall, W. L. J. Phys. Chem. 1968, 72, 684 703. Lukashov, Yu. M.; Komissarov, K. B.; Golubev, B. P.; Smirnov, S. N.; Svistunov, E. P. Teploenergetika 1975, 22, 78 81. Zimmerman, G. H.; Gruszkiewicz, M. S.; Wood, R. H. J . Phys. Chem. 1995, 99, 11612 11625. Gruszkiewicz, M. S.; Wood, R. H. J. Chem. Thermodynamics 1997, submitted. Pitzer, K. S. Acti ity Coefficients in Electrolyte Solutions. 2nd edition. Pitzer, K.S.: editor. CRC Press: Boca Raton, FL. 1991. Archer, D. G.; Wang, P. J. J . Phys. Chem. Ref . Data 1991, 19, 371 411. Levelt Sengers, J. M. H.; Everhart, C. M.; Morrison, G.; Pitzer, K. S. Chem. Eng. Commun. 1986, 47, 315 328. Levelt Sengers, J. M. H.; Harvey, A. H.; Crovetto, R.; Gallagher, J. S. Fluid Phase Equilib. 1992, 81, 85 107. OConnell, J. P.; Sharygin, A. V.; Wood, R. H. Ind. Eng. Chem. Res. 1996, 35, 2808 2812. Hnedkovsky, L.; Wood, R. H.; Majer, V. J. Chem. Thermodynamics 1996, 28, 125 142. Harvey, A. H.; Levelt Sengers, J. M. H.; Tanger, J. C., IV. J. Phys. Chem. 1991, 95, 932 937. Archer, D. G. J . Phys. Chem. Ref . Data 1992, 21, 793 829. Cooney, W. R.; OConnell, J. P. Chem. Eng. Commun. 1987, 56, 341 349.

(Recei ed 17 January 1997; in final form 19 May 1997)

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