0-502 J. Chem. fhermodynamics 1993, 25, 887-904 On the osmotic and activity coefficients of Na,WO,(aq) and Na,MoO,(aq) at the temperature 298.15 K, and the relations between mean activity coefficients of solutes under isopiestic conditions’ Joseph A. Rard Earth Sciences Division, University of California, Lawrence Livermore National Laboratory, Livermore, CA 94550, U.S.A. (Received 22 October 1992; in final form 21 December 1992) Wu et al. (J. Chem, Thermodynamics 1990, 22, 35) reported osmotic coefficients for Naz WO,(aq) and Na,MoO,(aq) at T= 298.15 K which were calculated from their isopiestic measurements, ‘They analyzed their results with a variant of the Gibbs-Duhem equation, and from those calculations obtained mean activity coefficients for the two electrolytes. Osmotic coefficients for both have highly anomalous dependences on molality, but no mention of this was made by the authors. The osmotic coefficients exhibit double minima followed by an approach to nearly constant values above molalities mx 2 mol-kg~'. These unusual features appear to be due to the onset of hydrolytic polymerization as the pHs of the solutions decrease as they are diluted, followed by depolymerization at low molalities. A detailed re-examination of these osmotic coefficients indicates that the mean activity coefficients of Wu et al. were incorrectly calculated and are too large by a factor of 1.5. In addition, their calculations involved integration of a function that diverges to — so as m—+0, which makes values of the integral highly uncertain. Furthermore, the unusual molality dependences of the osmotic coefficients preclude any meaningful extrapolations to infinite dilution, as are required for the calculation of reliable activity coefficients. A detailed analysis is given of the functional relations between the mean activity coefficients of two different solutes in separate solutions at isopiestic equilibrium. It is shown that the integral which appears in one equation, in the form in which it is usually written, has an integrand that diverges to +c or —oo as m0 for solutes of different charge types. However, that integral can be recast into a different form which has no divergences. 1. Introduction Experimental values have been reported that yield standard molar thermodynamic properties for most of the known oxyanions of the type XO2~(aq). Of those ions, = This document was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor the University of California nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial products, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or the University of California, and shall not be used for advertising or product endorsement purposes. 0021-9614/93/070887 + 18 $08.00/0 © 1993 Academic Press Limited888 JA. Rard only SO2-(aq) is sufficiently well characterized by a wide variety of concordant thermodynamic measurements to be included in the CODATA tables.’ Some measurements of this type are also available for the tetraoxometallate(2-) ions, of which WO3 (aq) and MoO} ~(aq) are of concern to us here. Dellien et al.?:) used experimental thermodynamic results for the dissolution of PbWO,(cr) and CaWO,(cr) in water at T = 298.15 K to derive values for the molar entropy S%(WO2-, aq, 298.15 K) of 25.59J-K~!+mol~! and 109J-K~'-mol7', respectively, but considered the latter value to be unrealistically large.®’ They” also noted that Latimer'*’ estimated a value of 63J-K~'-mol~! for that quantity. Dellien'®) subsequently recommended the value $2(WO32-, aq, 298.15K) = 40.7J-K-'-mol-', on the basis of his own isopiestic-type vapor-pressure measurements in combination with published calorimetric measurements. Dellien’s water vapor-pressure measurements were done for solid mixtures of Na,WO,(cr) and Na,;WO,*2H,O(cr) and for three molalities of Na,WO,(aq), all at T=298.15K. This impressive variation between calculated standard molar entropies is a consequence of inaccuracies in the experimental thermodynamic values, especially from uncertainties in the solubilities of PbWO,(cr) and CaWO,(cr). Standard molar thermodynamic properties for MoO3-(aq) have been the subject of more studies. Careful calorimetric measurements for the enthalpy of dissolution of MoO,(cr) in NaOH(aq), RbOH(aq),” and LiOH(aq),® yield an accurate and precise value of A,H2(MoO2-, aq, 298.15 K) = —(997.0+0.8) kJ-mol~!. O'Hare et al‘) have performed calculations using thermodynamic results for BaMoO,(cr), SrMoO,(cr), CaMoO,(cr), FeMoO,(cr), and Ag,MoO,(cr) that give the standard molar Gibbs free energy of formation 4,G2(MoO3-, aq, 298.15 K) = —(836.0+2.9) kJ-mol"!, and therefore’) $3(MoO2~, aq, 298.15 K) = (29+10)J-K~!-mol-!. Their calculations of the values of AyG3, and Sz, depend on the thermodynamic solubility products K° for the crystalline solid phases under consideration. O’Hare' cited two values for K° of BaMoO,(cr) that are within about 10 per cent, but for PbMoO,(cr) the variations are nearly a factor of ten.) Recent careful solubility measurements"° for CaMoO,(cr) yield a value of K° = 1.21078, which is about a factor of four larger than the value selected by O’Hare et al.'® Dellien et al. cited solubility studies for CaMoO,(cr) and BaMoO,(cr) that differ by about a factor of three to ten from values of K° selected by O'Hare et al.) In addition, by using different values of K° from the literature, Dellien et al.°) calculated values of S°(MoO3-, aq, 298.15 K) that range from 2J-K~!-mol-! to 43.1J-K~!-mol@*. They also noted that these large discrepancies arise in part because the degrees of crystallinity of the precipitates in the solubility studies may not correspond to those in calorimetric studies, and we note that some of the precipitated solids may have been partially hydrated. Activity coefficients are needed when Gibbs free energies are to be calculated from experimental solubilities. These activity coefficients can generally be estimated fairly accurately for sparingly soluble solutes, which is an advantage. However, as we have just observed, available values for K° of most of the molybdates under consideration are uncertain by up to a factor of ten, and an uncertainty of this size is probably the case for the tungstates. This magnitude of uncertainty gives an uncertainty in the@ and y of Na,WO,(aq) and Na,MoO,(aq) 889 values of S;, of R-In 10 = 19 J-K~!-mol~'. In contrast, solubilities of highly soluble salts can be determined much more precisely, and in principle could be used for the calculation of more reliable values of A,G, and $2, for WO2-(aq) and MoO3- (aq). Experimental activity coefficients are required, because they cannot be reliably estimated at such high molalities. The solubilities of Na;WO,-2H ,O(cr) and Na,MoO,-2H,O(cr) at T = 298.15 K are fairly accurately known; these are the solid phases that exist in equilibrium with their saturated aqueous solutions. They are also the only tungstates and molybdates that have been studied by the isopiestic method, and the only ones for which significant numbers of osmotic or activity coefficients are available. Literature values of the solubilities at T= 298.15 K were recalculated to the current IUPAC molar masses: 293.83 g-mol~’ for NayWO, and 205.92 g: mol” ' for Na,Mo0,. The recalculated solubilities are 3.155 mol-kg-1;4” 3.160 mol-kg~, 3.157 mol-kg~', and 3.179 mol: kg~3;"? 3.16 mol -kg~?;""9) 3.165 mol kgs" and 3.164 mol-kg~!"5!® for Na,MoO,(aq) with a mean value of (3.163+0.016) molkg~!. For Na;WO,(aq) the recalculated solubilities are 2.532 mol: kg~!,7 2.526 mol: kg~!,"'® and 2.395 mol-kg~1."°) This third value is somewhat discrepant. However, Linke“ tabulated solubilities for Na,WO,(aq) at various temperatures, from which we derive a solubility of 2.518 mol-kg~! by graphical interpolation to T = 298.15 K. The mean of the three values in agreement is (2.525 +0.014) mol-kg~'. Our reported uncertainties are 95 per cent confidence limits. These solubilities are uncertain by about 0.5 per cent, which contributes to uncertainties for K° of 1.5 per cent. Isopiestic measurements were reported at T = 298.15 K for three molalities from (1.29 to 3.16) mol-kg~? for Na;MoO,,(aq),"®) and at three molalities from (1.380 to 2.558) mol:kg~' for Na,WO,(aq),'® from which were obtained mean activity coefficients. After isopiestic equilibrium had been reached, the molality of each solution was determined by direct chemical analysis. Those results have much greater uncertainties (especially at the lower molalities) than those for experiments done with more traditional experimental techniques.?” Neither of these measurements extends to low enough molalities to allow the activities to be reliably extrapolated to infinite dilution, as is required for the calculation of activity coefficients. Goldberg‘? re-analyzed these isopiestic results for Na,WO,(aq) to obtain provisional values of the osmotic coefficient @, water activity a,, mean activity coefficient 7, and total excess molar Gibbs free energy. He also remarked that “Additional data would be desirable”, which is certainly the case. Wu et al.2”) have since reported much more detailed isopiestic results for both solutions at T= 298.15 K, with use of a traditional isopiestic apparatus. Those results range from (0.3051 to 2.5253) mol-kg~! for Na,WO,(aq) and (0.3102 to 2.3715) mol-kg~! for Na;MoO,(aq). From these isopiestic molalities they derived values of @, 7,, and excess molar Gibbs free energy G3. Theit results extend essentially to saturation for Na,WO,(aq) and to 75 per cent of saturation for Na,MoO,(aq). If their measurements were reliable, they could yield quite precise molar Gibbs free energies of solution of Na,WO,-2H,O(cr) and Na,MoO,:2H,O(cr). However, Wu et al. noted that their derived values of 7,890 J. A. Rard disagreed with values derived from the earlier isopiestic studies,°-'*:?" and attributed these differences mainly to the earlier studies having too few molality points to yield meaningful results. Robinson and Sinclair'?*) reported the results of isopiestic measurements at three concentrations of Na,WO,(aq) and one of Na,MoO,(aq), and a greater number of results for mixtures of those salts with HCl. None of the other reports'*: 19:21:22) referenced the Robinson and Sinclair paper. We re-examined in detail all of these isopiestic results to see whether they could be used to derive reliable values of a,, 7,, and A, Gs, with emphasis on the more extensive results of Wu et al/2?) We conclude, based upon the highly anomalous dependences of @ on molality, that hydrolytic polymerization occurs below mx 1 mol-kg~' for both solutions. Because of this, no meaningful values of y, can be derived from the published isopiestic results. 2. Reanalysis of published isopiestic molalities We recalculated values of ¢ from the reported isopiestic molalities insofar as this was possible. Zhidikova et al.) did their isopiestic equilibrations against NaCl(aq) as isopiestic reference standard, and the measurements of Dellien® were relative to H,SO,(aq). In both of those studies the results were given as values of m, ay, and ¢, along with their associated uncertainties, but the molalities of the reference standard solutions were not reported. We recalculated values of ¢ and 8¢ from the reported molalities and a,, values, as described immediately below. The relation between ¢ and a, is given by: Ina, =—vmM,,¢, qa) where m is the molality of Na,WO, or Na;MoO,, M,, = 0.0180153 kg: mol! is the molar mass of HO, and v=3 is the stoichiometric ionization number for these electrolytes assuming they dissociate as strong 1-2 electrolytes. Errors in @ were calculated from those of a, and m by use of standard propagation-of-error techniques: BH = {(5G)?} 41? = (1/m){(1/9M3)(8ay/ay)? + 67(5m)?} 1. Q) We note that for isopiestic measurements, the term involving 5a, dominates the error calculations. Our derived values of @ and 8¢ agree well with those reported by Zhidikova et al. and Dellien.” Both Robinson and Sinclair?) and Wu et al.??) did their measurements relative to KCl(aq) as isopiestic reference standard. Wu et al. also equilibrated their samples simultaneously against NaCl(aq) as a second reference standard, but did not report those NaCl(aq) molalities. Values of ¢ for Na,WO,(aq) and Na;MoO,(aq) were recalculated from these isopiestic molalities and the ¢* values for KCl(aq) of Hamer and Wu* using the fundamental equation for isopiestic equilibrium: b = vim*b*/vn, 3) where * denotes the reference standard and v* = 2 for KCI. We note that Robinson@ and y of Na,WO,(aq) and Na,MoO,{aq) 891 and Sinclair reported isopiestic concentrations rather than molalities. The concentration-to-molality conversions used the density equation for KCI(aq) from Rard and Miller,2®) and for Na;WO,(aq) and Na,MoO,(aq) the apparent molar volume equations of Olofsson et al.?° Robinson and Sinclair? did not report the precisions of their isopiestic results, but we estimate the precision of ¢ from their study as being about 0.003. Wu et al.(2?) used single samples of each electrolyte, so the precisions of their m and m* are unknown. However, they did state that values of a, calculated from the molalities of KCI and NaCl agreed to 0.0003 or better, so we calculated values of 8¢ assuming that value for 5a,. At least at lower molalities, the smoothness of these $s is better than indicated by our error calculations. Tables 1 and 2 summarize all of the recalculated isopiestic results for Na,WO,(aq) and Na;MoO,(aq) at T=298.15K, and figures 1 and 2 compare these results TABLE 1. Recalculated isopiestic results for Na,WO,(aq) at T= 298.15 K mAmol-kg~*) a 6 (omy/m®){(2n/3m) — 1} /mity’t) 0.0865" 0.99599 0.8599 0.0912 —0.7478 00977" 0.99547 0.8598, 0.1020. —0.6454 0.3081" 0.9861 0.8383 0.2836 —0.2476 1,380 + 0.002° 0.938 +.0.002 0.8582+ 0.0286 1.846 +0.002° 0.913+0,001 0.9123+0.0110 2.558 +0.003° 0.875+0.001 0.9659 +0.0083 0.3051 0.9872 +0.0003 0.7802 + 0.0184 0.2635 0.3790 0.9837 + 0.0003 0.8018 +0.0149 0.3283 0.4603 0.9798 +0,0003 0.8188 +0.0123 0.3985 0.5496 0.9758 40.0003 0.82444 0.0104 0.4701 0.6408 0.9719 + 0.0003 0.8218 + 0.0089 0.5381 0.7335 0.9682 +.0.0003 0.8144+0.0078 0.6026, 0.8143 0.9654 +0.0003 0.8005 + 0.0071 0.6517, 0.8613 0.9640 + 0.0003 0.7882 +0.0067 0.6759 0.9012 0.9626 +. 0.0003 0.78224 0.0064 0.6992 0.9363 0.9608 + 0.0003 0.7911 40.0062 O7311 1.0704, 0.9547 +. 0.0003 0.8105 +0.0054 0.8346 1.2034 0.9486 + 0,0003 0.8121 +0.0049 0.9388 1.3635 0.9411 + 0.0003 0.8243 + 0.0043 1.0658 1.4671 0.9352 + 0.0003 0.8443 +.0.0040 1.1644 1.5716 0.9286 +.0.0003 0.8719 +0.0038 1.2772 1.6420, 0.9225 + 0.0003 0.9092 + 0.0037 13819 1.6493 0.9211 +.0.0003 0.9225 +.0.0037 1.4063 1.7351 0.9164 +4 0.0003 0.9309 + 0.0035 1.4862 1.9340 0.9051 + 0.0003 0.9541 + 0.0032 1.6822 2.1031 0.8963 + 0.0003 0.9632 + 0.0029 1.8359 2.3790, 0.8834 +. 0.0003 0.9644 +. 0.0026 2.0659 2.5253 0.8750 40,0003 0.9783 +0.0025 2.2174 * Isopiestic molalities of Robinson and Sinclair!» relative to KCl(aq) isopiestic reference standards. 'Isopiestic results of Dellien'* relative 19 H,SO,(aq) isopiestic reference standards. Results were presented by him as values of a,, and the H,SO,(aq) reference standard molalities were not reported. « Here and below are the isopiestic results of Wu et al!?” relative to NaCi(aq) and KCi(aq) isopiestic reference standards, They did not report the NaCi(aq) molalities. Error limits were calculated by assuming that a, was uncertain by 0.0003, which is their claimed maximum uncertainty.892 JA. Rard TABLE 2. Recalculated isopiestic results for Na,MoO,(aq) at T = 298.15 K m/(mol-kg~*) ae ¢ (my n°) {(2m*/3m)— 1}(m°/m*y) 0.1604¢ 099338 0.7666 0.1447 1.1089 129° 0.924 +0.008 1.1337 40.1243 220" 0.880 + 0.003 1.0751 £0.0288 3.16* 0.8205 40.0005, 1.1584 0.0040 0.3102° 0.9872 + 0.0003 0.7674 +0.0181 0.2635 0.3819 0.9837 +.0.0003 0.7957 + 0.0148 0.3283 0.4608 0.9798 + 0.0003 0.8179 40.0123 0.3985, 0.5481 0.9758 + 0.0003 0.8266 + 0.0104 0.4701 0.6391 0.9719 +0.0003, 0.8240 0.0089 0.5381 0.7310 0.9682 + 0.0003, 0.8172 + 0.0078 0.6026 0.8135 0.9654 +-0.0003, 0.8012 +0.0071 0.6517 0.8603 0.9640 + 0.0003 0.7891 0.0067 0.6759 0.9003 0.9626 + 0.0003 0.7830 + 0.0064 0.6992 0.9344 0.9608 0.0003 0.7927 + 0.0062 07311 10818 0.9547+0.0003, 0.7931 +0.0054 08346 1.2237 0.9486 + 0.0003 0.7987 + 0.0048 0.9388 1.3670 0.9411 40.0003 0.82224 0.0043 1.0658 ~0,0899 1.4607 0.9352 40.0003 0.8480 + 0.0041 1.1644 — 0.0610 1.5531 0.9286 + 0.0003 0.8823 + 0.0038 1.2772 — 0.0298 1.6476 0.9225 + 0.0003 0.9061 40.0037 13819 0.0121 1.6871 0.9211 +0.0003 0.9019 +-0.0036 1.4063 —00159 1.7410 0.9164 40.0003 0.9278 + 0.0035 1.4862 0.0013 1.9410 0.9051 + 0.0003 0.9507 + 0.0032 1.6822 0.0101 2.1205 0.8963 + 0.0003 0.9553 40.0029 1.8359 0.0076 23715 0.8834 + 0.0003 0.9674 + 0.0026 2.0659 0.0073 * Isopiestic molality of Robinson and Sinclair?» relative to KCl(aq) isopiestic reference standard. * Tsopiestic results of Zhidikova et al." relative to NaCi(aq) isopiestic reference standards. Results were presented by them as values of a,, and the NaC\(aq) reference standard molalities were not reported. © Here and below are the isopiestic results of Wu et al.” relative to NaCl(aq) and KCl(aq) isopiestic reference standards. They did not report the NaCl(aq) molalities. Error limits were calculated by assuming that a, was uncertain by 0.0003, which is their claimed maximum uncertainty. graphically. The straight lines are the Debye~Hiickel limiting law for ¢: $ou = where A = 0.51082-2-(3)'/?-In 10 mol"? kg'? = 4.0744 mol-"/?-kg'/?_ is _ the Debye-Hiickel limiting slope for an aqueous 1-2 electrolyte. Also plotted (dashed curves) is the Debye-Hiickel “osmotic” equation for a 1~2 electrolyte in the universal form recommended by Pitzer:?” —(A/3)m'?, (4) dono = 1—2A491'7/(1 + BI"), (5) where A*=0,3915mol-!?-kg'?, 1=3m is the ionic strength, and b= 1.2mol-!/?- kg!/?, Clearly, the experimental values of ¢ do not approach ¢py or @pxo at the low molalities. From figure | it is clear that the @ values of Dellien‘®’ are in general agreement with those of Wu et al.,??) with two of Dellien’s three points agreeing to just withinand 7 of Na, WO,(aq) and Na;MoO,(aq) 893 0 O25 O50 Oly 1 OO ies sg 5 (mA mot-kg"')} FIGURE 1. Values of @ as a function of m'/? for Na,WO,(aq) at T = 298.15 K. ——, Debye-Hiickel limiting law; — — —, Pitzer’s Debye-Hiickel “osmotic” equation; , Robinson and Sinclair’? O, Wu et al? ©, Dellien. 1.0) s 08 0 02 050075 100SCOSSSC*CSSSC*SC«STSN {mimor-kg')} FIGURE 2. Values of # as a function of m' for NayMoO,(aq) at T = 298.15 K, -—, Debye-Hiickel limiting law; — ——, Pitzer’s Debye—Hiickel “osmotic” equation; @, Robinson and Sinclair;??” ©, Wu et als? ©, Zhidikova et al.894 JA. Rard the combined experimental uncertainties. Differences between the results of these two studies range from 0.015 to 0.03, or 0.016-@ to 0.04. However, the s of Robinson and Sinclair?” are significantly higher than the lower-molality @ values of Wu et al. These two sets of ¢ values probably would have merged or crossed at m= 0.5 mol: kg~! had Robinson and Sinclair extended their measurements to higher molalities. An examination of the plot for Na,MoO,(aq), figure 2, indicates that ¢ values of Zhidikova et al.) are considerably higher than those of Wu et al.22) by about 10 per cent to 40 per cent, and this difference greatly exceeds the combined estimated experimental uncertainties. We consider the values from Wu et al. to be more reliable in view of their much better precision. The one value of @ from Robinson and Sinclair?» is similar in magnitude to the values of Wu et al., but there is no overlap in molality, so their consistency cannot be checked. The values of for Na,WO,(aq) and Na,MoO,,(aq) from Wu et al?! have highly anomalous molality dependences. First, the ¢ curves both have a minimum at m= 0.9 mol-kg~!, and each must possess at least one additional minimum below mx 0.3 mol-kg~', but the measurements did not extend to low enough molalities to define that region. Secondly, @ curves for both salts have a relative maximum at m~0.Smol-kg~!, and approach a plateau or a second maximum at mx 2.5 mol-kg~!. We refer to these curves as having a skewed W shape. We are unaware of any other systems with such peculiar molality dependences. Plots of # against m'/? for aqueous strong electrolytes nearly always have a single featureless minimum followed by a more or less gradual rise with increasing molality. A few extremely soluble electrolytes such as CaCl,(aq) and HSO,(aq) ultimately reach a maximum in @ followed by a gradual decrease. A very shallow double minimum has been reported for ¢ of ZnCl,(aq)2" about 0.001, which is much smaller than the minima for Na,;WO,(aq) and Na,MoO,(aq). This double minimum for ZnCl,(aq) was attributed to the sudden onset of significant complex formation at mx(0.1 to 0.2)mol-kg~'.2® Rather different types of equilibria seem to be responsible for the skewed W shapes for @ of Na,WO,(aq) and Na,MoO,(aq). The pH of saturated Na,WO,(aq) at T=298.15K has been reported to be 10.15,¢ and 7.5, and that of saturated Na,MoO,(aq) as 9.06," 8.71,15) 9.39,09 9.65,29' and 9.16.9” Although these pH values indicate that the solutions at their “natural” pHs are fairly alkaline, the variations imply that what passes for stoichiometric Na;WO,(aq) and Na,MoO,(aq) have some variation from exact stoichiometry due to a slight excess or deficiency of NaOH. As the solutions are diluted with water during the isopiestic experiments, their pHs gradually approach pH =7 of pure water. In very dilute solutions, the tungstate and molybdate ions are extensively hydrolyzed to form the monomeric species HXOj(aq) and H,XO,(aq). At m= 0.901 mol-kg~! or higher molalities, however, the predominant hydrolysis reaction for molybdate is: 7Mo0}3 (aq) + 8H*(aq) = Mo,0$4(aq)+ 4H O(sin), (6) with further protonation and polymerization occurring if the pH is decreased below@ and y of Na,WO,(aq) and Na,MoO,(aq) 895 about 6.°!-32) Reported values of the apparent equilibrium constant for equation (6) range from lg K = 52.45 to lg K = 57.71” for concentration-based ionic strengths of (06 to 3.0) mol-dm~, and vary both with ionic strength and ionic medium. A more extensive tabulation’ lists values ranging from Ig K = 51.37 to lg K = 60.17. Numerous other polymers which contain up to 36 molybdenum atoms have been claimed to form at pHs below about 5 or 6, but not all of them really exist. The Gmelin Handbook» gives a detailed listing of these proposed species, along with a tabulation of published protonation and polymerization constants. The hydrolytic polymerization of WO327(aq) has been the subject of fewer studies. A recent n.m.r. investigation? led to the plausible conclusion that the predominant hydrolyzed polymers which form in the pH range of 5 to 9 are W,O%; (paratungstate A) and H,W,,04$~ (paratungstate B). That study was done at total tungstate concentrations of about 2 mol-dm °. As noted by Wesolowski et al.,'** potentiometric measurements alone are not always able to discriminate between alternative combinations of proposed species with similar degrees of polymerization or protonation. Thus, they do not provide unique and unambiguous formulations for the hydrolyzed polymers. The n.m.r. measurements'*) yield less equivocal results. Because of these molality and pH-dependent equilibria, it is not surprising that values of @ show such complicated molality dependences. It is likely that the presence of the maxima at m= 0.5 mol-kg~! and the minima at m~0.9 mol-kg"! for both solutions is due to the occurrence of these hydrolytic polymerization reactions. The presence of hydrolytic polymerization affects values of ¢ in three ways. First, changes in speciation affect } directly because they affect a,, and these two quantities are interrelated by equation (1). Although the hydrolyzed polymers have greater negative electrical charges than the XO2 (aq) monomers from which they were formed, that charge is spread out over much larger ions and thus the surface charge densities are lower than for the monomeric ions. Consequently, the overall hydration of ions such as X;0$; (aq) should be less than the overall hydration for seven equivalent monomer units of XO3-(aq). Polymerization should thus increase the values of a, (and lower the values of ¢) relative to the hypothetical fully monomeric electrolyte at the same molality. Secondly, ion pairs of the type NaXO,(aq) and KXO,(aq) are known to form in solutions of the alkali-metal sulfates: M*(aq)+XO3-(aq) = MXOj (aq), a and the stoichiometric formation constants for them are about (10 to 12) mol-!-kg.?*) Similar ion pairs NaWO;(aq) and NaMoO;(aq) are probably present in solutions of the stoichiometric salts. The large variation in formation constants for reaction (6) with different ionic media'*?"3» may indicate in part that significant ion-pair formation occurs between Na*(aq) and X,0$;(aq). If present, such ion pairs will influence values of @ in two ways. One way is by increasing a, and decreasing ¢ due to reduced ion-solvent interaction because ion pairing reduces the charges on the ions. The other way is by reducing the number of ions in solution.896 J.A. Rard Because values of ¢ are calculated with the stoichiometric values of the “osmolalities”, and the true “osmolalities” are less than these, the apparent values of @ will be too small. This results because the product of the “osmolality” and ¢ is invariant as indicated by equation (1). Whether this actually causes the apparent values of @ to increase or decrease for a polymerized electrolyte relative to the monomeric electrolyte will depend on whether these ion pairs are more extensive for the polymer or monomer. The high charge on the polymeric anions should certainly be conducive to enhanced ion-pair formation. Thirdly, and most importantly, there is a change in the total number of ions in these solutions due to the hydrolytic polymerization. We will now derive the relation between the stoichiometric ¢ value and the osmotic coefficient $, calculated with actual speciation present in the solutions at equilibrium. Because the solutions used for these isopiestic studies were at pH > 7, it is more useful to rewrite the hydrolytic polymerization reactions as hydrolyses rather than protonation reactions. We shall restrict our discussion to a simplified case involving formation of one type of polymer: TXO}-(aq) + 4H, 0) = X,0$;(aq) + 80H “(aq)- 8) The value of a, for a solution of Na;XO, at any particular molality is independent of assumptions about speciation. However, as can be seen from equation (1), = (in a,)/My = mg = Vive de, 9) and thus numerical values of the osmotic coefficient depend on molalities of the ions, whether stoichiometric or actual. The sum of the actual ionic molalities (“osmolalities”) in these solutions will be given by the equation: Lavum)e = m(X;O$4) + (OH) + m(XOF-) + m(Na*), (10) provided that association of Na*(aq) with the anions can be neglected. Clearly, m(Na*) is twice the stoichiometric molality. The total amount of W or Mo does not change, so {7m(X,0$5)+m(XO3~)} must equal the stoichiometric molality m, and m(OH -) = 8m(X,08,) if the self-dissociation of water can be neglected. Combining these relations then yields: Livan) e = 3m+ 2m{X 044). a1) Inserting this equation into equation (9) gives: 4 = [(3m + 2m(X,034)}/3m] be (12) At any finite molality $>,, so any change in speciation due to hydrolytic polymerization causes the stoichiometric ¢ values to increase. It is now possible to account for the observed qualitative features of the molality dependences of ¢ for Na,WO,(aq) and Na,MoO,(aq) as illustrated in figures 1 and 2. The initial decreases in ¢, which occur well below the molality ranges studied by Wu et al.{??) are partly due to the usual long-range electrostatic forces and ion-solvent interactions. However, the decrease in ¢ will be a little more rapid here than for a highly dissociated 1-2 electrolyte because of partial hydrolysis to form@ and y of Na,WO,(aq) and Na,MoO,(aq) 897 HXO, (aq). As the molality increases above m= (0.2 to 0.3) mol-kg~!, hydrolytic polymerization becomes very important and gives rise to an increase in ¢. Furthermore, as the molality increases, so do the pHs of the solutions, which ultimately causes the polymers to redissociate to XO2-(aq) monomers. This in turn causes @ to reverse direction and to start decreasing after going through a maximum. Isopiestic results are available for several alkali-metal salts of the types M,SO,(aq) and M,CrO,(aq). Osmotic coefficients for Li,SO,4(aq), Na,SO,(aq), NaCrO,(aq), and K ,CrO,(aq) each go through a featureless minimum and then increase at higher molalities.?" Thus, the increase in ¢ above m~ 1 mol-kg~! for NayWO,(aq) and Na,MoO,(aq) is normal and expected for monomeric Na,XO,(aq). It is possible to model reliably the activities of electrolyte solutions with multiple equilibria, provided the appropriate equilibrium constants are accurately known.) Unfortunately, the equilibrium constants for the hydrolytic polymerization of WO3 (ag) and MoO}-(aq) are uncertain by many factors of ten and the pHs of the solutions are unknown, so that at present, this approach cannot be used for Na,WO,(aq) and Na,MoO,(aq). Based upon the discussion given in this section, we conclude that meaningful activity coefficients cannot be obtained from the isopiestic study of Wu et al.{?? or from the other published isopiestic results!3-29 for Na,WO,(aq) and Na,Mo0O,(aq). However, if isopiestic or e.m.f. measurements were to be done for mixtures of {yNa,XO,+(1—y)NaOH}(aq) with sufficient OH (aq) present to suppress hydrolytic polymerization, meaningful activity coefficients could be extracted for solutions of unpolymerized Na,XO,(aq) We note that Wu et al.) “purified” their Na;WO, and Na,MoO, samples by recrystallizing them twice from water. This process probably reduced the normally alkaline “natural” pHs of their solutions, and thus exacerbated the extent of hydrolytic polymerization. That effect could have been reduced by doing the recrystallizations from dilute NaOH(aq) solutions instead. We believe that the large differences between the ¢ values of Wu et al.'2? and of Robinson and Sinclair’? for Na,WO,(aq) are most likely due to differences in pH. 3. A stratagem for calculation of activity coefficients Wu et al? made no mention of the unusual molality dependences of @ for Na,WO,(aq) and Na,MoO,(aq), nor did they give plots of the ¢ values. However, they must have recognized the difficulty with trying to extrapolate their results to infinite dilution because they used a different approach to calculate activity coefficients. Their method of calculation involved the “isopiestic ratio” & = v*m*/um, (13) where molalities refer to solutions at isopiestic equilibrium (i.e. with equal water activities). This approach involves relating values of y, for the solution of interest to the corresponding 7 of the isopiestic reference standard under isopiestic conditions.898 JA. Rard The equation given by Wu et al.,?” after recasting it into our notation, is (any? Iny, = In y} +In(n*/m) +2 [ (@-1ylaty'?} ata)”, (14) ° where a* is the thermodynamic activity of the isopiestic reference standard. They did not give any details as to how the integrals were evaluated, whether graphically, numerically, or analytically. This equation is incorrect, as we show below. A correct special case of equation (14) was first derived by Robinson and Sinclair,?® but with the isopiestic molality ratio (m*/m) appearing in the integrand rather than the “isopiestic ratio” @. However, their derivation was restricted to solutions of 1-1 electrolytes in isopiestic equilibrium, and it is not generally valid for electrolytes of other valence types. The more general form of that equation has been reported in the literature: see, for example, Hamer and Wu? and Robinson and Stokes.°° Pitzer and Brewer*® give an equivalent form in terms of m*)* rather than a*. However, one significant difference exists between the equation of Wu ef al?) and the forms given elsewhere:?+2%-*® the second term on the right-hand side of equation (14) is given as In(m*/m) by Wu et al. and as In@ by the other authors. The difference between (m*/m) and & is 2/3 for the systems studied by Wu et al., and their reported values of >, should be reduced by this factor, Making this correction greatly reduces the discrepancies between their?” reported values of » , and those given by Goldberg?” for Na;WO (aq). To verify that Wu et al.2”) made an error, we sketch a derivation of the correct form of equation (14). The Gibbs-Duhem equation can be written as: *-dIna*, (15) —ny-dInay =n-dina =—nt-dIn ak = for two binary electrolyte solutions in isopiestic equilibrium. Here, n, and n% are the amounts of H,O in the solutions and n and n* are the amounts of the solutes. The relation between solute activities, molalities, and activity coefficients yields d In a = v-d In(my,) and d Ina* = v*-d In(m* Also, the ratio of the amounts of substance n*/n will equal the molality ratio m*/m. Then equation (15) takes the form vin: d In(my..) = vém*-d In(m*y4). (16) Rearranging the equation gives: din y, =—d In m+(v*m*/vm)d In(m*y?), (7) and, after replacing (v*m*/vm) by @ and making some straightforward algebraic manipulations: din yp, =d In yt $d In(m*/m) + {(B— lyfmy%} dy). (18) The desired equation is obtained by integration of this equation from infinite dilution to the molalities of interest, m and m*. Integration of the activity-coefficient terms from infinite dilution gives In(y,/1)=Iny, and In(t/1)=Iny%, and integration of the second term on the right-hand side of equation (18) yields@ and y of Na;WO,(aq) and Na;MoO,(aq) 899 0.2 ok e002 © oo | ° ° Ge z 00% 2 oak 4 = ae & i ° ae 2 -04b 4 g 4 ° ~ ~0.6F 4 “ a -08 0 05 10 15 20 ZS (yin) FIGURE 3. Values of (@—1Xm*/m*y$) = ((2m*/3m)—1}(m°/m*yt) as a function of (m*yt/m°) for Na, WO.,(aq) with KClfag) as isopiestic reference standard at T= 298.15 K, a, Robinson and Sinclair;?? O, Wu et ali?) In{(m*/m)/lim,,,»_.o(t*/m)}. Both m* and m approach zero under isopiestic conditions. By equation (3), and recognizing that both and $* approach I as m and m* go to infinite dilution, lim, m+ .o(*/m) = v/v*. Thus, these results yield: mt Iny, =InyE +n A+ j {A Mylmry} dont y%), a9) ° which confirms that the equation of Wu et al.2”) is missing a factor (v*/v) = 2/3 in the second term past the equal sign.+ Tables 1 and 2 contain values of the integrand of equation (19) for the isopiestic results of Wu et al.2?) and Robinson and Sinclair{?*) where y* for KCl was calculated from the equation of Hamer and Wu.?* No such calculations could be done for the results from the other two studies‘) because the reference standard molalities were not reported. Figure 3 is a plot of these values of {(2m*/3m)—1}(m?/m*y*) against (m*y%/m°) for Na,WO,(aq), where m° = 1 mol-kg~'. The analogous curve for NayMoO,(aq) (not given) is very similar in appearance. The abscissa of this curve is the integrand of equation (19). That function shows little variation with molality for (m*y*/m°) > 0.5. Below that value the curve descends steeply, but there are few points to define the curvature. Both (@—1) = {(2m*/3m)—1} and m*y* go to zero at infinite dilution, so + If this equation is rewritten in terms of (a*)"? rather than m*y*, then the integral will have a factor of two in front of it.900 J.A. Rard their ratio approaches the ratio zero over zero, but they do so under isopiestic conditions. It is necessary to obtain the limiting value of the integrand {(#—L/m*y*t} of equation (19) to see whether or not it becomes infinite at infinite dilution. This is most conveniently done by rewriting the expression for the integrand in terms of osmotic coefficients rather than the “isopiestic ratio” By combining the definition of # in equation (13) with the fundamental equation for isopiestic equilibrium equation (3), we obtain: R= olor. (20) Thus, the integrand of equation (19) can be rewritten as {(¢—$*)/(m*G*y*)}. The factors * and * in the denominator do not cause a problem, because both become equal to unity at infinite dilution. We still need to determine what happens to {(¢—$*)/m*} as the molalities go to zero. We assume that the molality dependences of the osmotic coefficients of each solution can be written as a Debye—Hiickel limiting-law term, equation (4), plus a series in various powers of molality, with molality to the power | as the leading term. Then, o-o* (1-(A/3)m"? + Amt +} — {1 (44/3? + At +} (1/3) A*(m*)"2 — Am™?} + (A,m— Atm*)+ higher order terms. (21) As both m and m*-+0, these higher-order terms rapidly go to zero and only the first two sets of terms in equation (21) need to be retained. We now evaluate the limit: Titty, me. (# ~ Ljn*74)} = lity, ne .of(b — b*(m*o*74)} = Hing, me of — b*)/m*} = limy, me-soL(1/3}{A* on")? — Am*?} + (Aym— Af m*)]/m*. (22) Two separate cases need to be considered. First, let both electrolytes be of the same charge type. Then, 4=A* and { A*(m*)!? — Am"/?} goes to zero at infinite dilution. The last term of equation (22) is {A,(m/m*) — A}, which has the limiting value {4,(v*/v)— 4%} =(4,— 49) for this case. Therefore, Tim,,, meso {(F — Dim*yt} = A, — AF, (23) and thus the integrand of equation (19) has a finite value at infinite dilution. We note that Robinson and Sinclair?* assumed that the lower limit for the integrand of equation (19) was zero for all alkali-metal chlorides. From equation (23) we see that this is true only if A, and 4* are accidentally equal, which is generally not the case. However, (A, — 4*) will usually be small (cither positive or negative) for chemically similar systems. In general, At and the higher-order coefficients will be known for the molality dependence of $*, and the corresponding coefficients for the electrolyte being studied can be obtained by a least-squares analysis of the experimental @ values. However,@ and 7 of Na,WO,(aq) and Na,MoO,(aq) 901 the coefficient A, of the equation for ¢ depends mainly on lower-molality results, and it may not always be adequately determined by isopiestic results alone. The procedure described in the next section does not require a value for A, and thus should introduce much less uncertainty when evaluating the integral of equation (19). Secondly, consider the case where the two electrolytes are not of the same charge type. For that case, the terms containing m!!? and (m*)"? in equation (22) do not cancel at low molalities and, instead, the function in equation (22) diverges to 00 or — 0. The two solutions of interest to us are Na, WO,(aq) and Na,MoO,(aq) which are 1-2 electrolytes, and KCl(aq) as reference standard. For salts of these charge types, (4/A*) = 2-(3)"?? = 3.4641. Consequently, the term {A*(m*)"”?— Am"? of the last line of equation (22) will always be negative for these solutions, and the integrand of equation (19) will thus diverge to —oo at m=0 and m* =0. We note that the experimental results of Wu et al.,2”) as plotted in figure 3, are clearly trending in that direction. Next, we do the same type of analysis with use of Pitzer’s equations” for @ and #*, rather than using equation (21). With Pitzer’s equations, and for electrolytes of the same charge type, the lowest-order non-zero term is: {@— Sym pry} (2v,v./v){(m/m*)B* —(B*)*}, (24) where v, and y, are the stoichiometric ionization numbers for anion and cation, respectively, and both B* and (B*)* depend on ionic strength. The limit of this function as m, m*=0 is (2v,v_/v)(B — BX + BO —B*™), Thus, the limiting value of the integrand of equation (19) remains finite and, in general, non-zero, just as it was when the extended Debye-Hiickel limiting-law expression was used. If the same type of derivation is performed for electrolytes of different charge types in isopiestic equilibrium, then the limit of the integrand in equation (19) at m= 0 and m* =0 becomes infinite for Pitzer’s equations. That behavior is essentially identical to that observed with use of the Debye-Hiickel limiting law with higher-order terms. We note that Pitzer and Brewer'*® did a related derivation with a different extended Debye-Hiickel equation for 1-1 electrolytes and similarly found that the integrand of equation (19) approached a constant value at m=0 and m*=0. However, we are unaware of any previous reports of the divergence of the integrand of equation (19) at m=0 and m* = 0 for two electrolytes of unequal charge type. Wu et al.??) had to evaluate the integral in equations (14) or (19) in order to calculate their values of activity coefficients. However, as we have just seen, that integrand diverges to — oo for their systems. Consequently, the value of this integral cannot be evaluated reliably, and that part of their calculation must be untrustworthy. 4. A related computational procedure without divergence problems By making a further transformation of the term under the integral sign in equation (19), we obtain a function that does not diverge to 00 or — 00 as m, m*0 for solutes of unequal charge types.902 JLA. Rard First, we use the relation: d(m*yby(m*yt) = d In(m*yt) = 2-d In(m*y*)!? = 2-d(mt yt) 2 /(mryty'?. (25) Secondly, we assume that (6—#*) can be represented by equation (21) at low molalities and that higher-order terms can be neglected. The quantity behind the integral of equation (19) thus takes the form: (A lylln*y)} dont 72) = [Ab — PO G*onty 7} 1 damty ty? & {2/B* (79)? }L(/3){ 4 — Arn) ?} + {Ap mj)? — As(m*)?})] dont yt)? (26) For two electrolytes of the same charge type, {A* — A(m/m*)'/2} 0 as m, m*—0, as does the sum of the remaining terms within the square brackets in equation (26). Thus, this function goes to zero at infinite dilution and it can be used for evaluation of the integral and thus the calculation of activity coefficients by equation (19). For electrolytes of unequal charge types, the function in front of the differential on the right-hand side of equation (26) approaches the limiting value: Titty, me sof AR — Ulm y¥)"2} = (2/3) * (v/v)? A}, 7) which has a finite numerical value. Consequently, it is suitable for use in the evaluation of activity coefficients by equation (19). For the electrolytes studied by Wu et al,,2? (2/3) A* —(w¥/vp!2 A} (mm)? = (2/3){ 1.1762 —(2/3)4!7(4.0744)} = — 1.4337. In this dissertation, Pan'*'’ gave a derivation of equation (27), but he restricted his equations for ¢ and $* to the Debye—Hiickel limiting law py, our equation (4). Figure 4 is a plot of the quantity in front of the derivative on the top line of the right-hand side of equation (26) for the two sets of isopiestic results for Na,WO,(aq) with KCi(aq) as reference standard. The results of Robinson and Sinclair? appear to approach the theoretical intercept for a strong 1-2 electrolyte at low molalities, but there are too few points to be sure. In contrast, the results of Wu et al.,?”) when extrapolated to lower molalities, appear to be headed below that theoretical intercept. From examination of this figure and the other ones, it appears likely that the electrolyte solutions of Wu et al. were more extensively polymerized than those of Robinson and Sinclair. We had reached the same conclusion at the end of section 2, based on their reported methods for solution preparation. Also plotted in figure 4 is the same function for MnCl,(aq) and RbCl(aq) with NaCl(aq) as isopiestic reference standard. The isopiestic molalities are taken from the study of Rard,¢?) and ¢* and y% are from Hamer and Wu.?* These curves for MnCl,(aq) and RbCi(aq) are simple smooth functions of (m*y*)!”?, in contrast to the curves for Na,WO,(aq) and Na,MoO,(aq), which have much structure. Even though the intercepts of this function are known at (m*yt)!? = 0 and depend only on the valence types of the electrolytes, the experimental curves do not¢ and 7 of Na,WO,(aq) and Na,MoO,,(aq) 903 0.5 1.0 (ry timey FIGURE 4. Values of 209 —I)(m' mt yt)!? = 2{(2mt/3m)— 1}(mr° my)! as a function of (m*yf/m?)" for Na,WO,(aq) with KCl(aq) as reference standard at T= 298.15K. &, Robinson and Sinclair?” Q, Wu et al.°? For comparison, this same function is also plotted for two strong electrolytes: Cl, MnClaq) with NaCl(ag) as reference standard:*?) @, RbC\aq) with NaCl(aq) as reference standard.“ For MnCl,(aq), # = 2m*/3m, but for RbCl{aq), #=m*/m. The theoretical intercept for Na,WO,(aq) and MnCl,(aq) from the Debye~Hiickel limiting law is marked with an arrow. approach those intercepts at the lower molalities when the electrolyte being investigated and its reference standard are of different charge types. The isopiestic method is not accurate enough below m=0.1 mol-kg~! to constrain such a plot, and it needs to be supplemented by some other type of measurement at lower molalities. In contrast, when both electrolytes are of the same charge type, that function approaches the intercept (zero) more closely, and it could be extrapolated accurately to m = 0 and m* =0 as shown by the curve for RbCI(aq). Thus, it could be used for calculation of accurate y, values. This work was supported under the auspices of the Office of Basic Energy Sciences (Geosciences) of the U.S. Department of Energy by the Lawrence Livermore National Laboratory under contract No. W-7405-ENG-48. The author thanks Donald G. 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