Thermochemistry of the liquid bismuth(lll) oxide - boron oxide: a new solvent for oxide melt solution calorimetry

Jacques Rogez and Jean Claude Mathieu

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Abstract: In solution calorimetry, the choice of solvent is important. Some criteria for this choice for oxide melt solution calorimetry are reviewed. A new solvent is proposed and the corresponding physicochemical study is presented. Some structural interpretations are suggested for these Bi203-B203 melts.

Key words:thermochemistry, calorimetry, high temperature, oxide melt.

RCsume : En calorimCtrie de dissolution le choix du solvant est important. Quelques ClCments de ce choix sont revus. On propose un nouveau solvant et son Ctude physicochimique est prtsentte. Des interpretations structurales sont suggtrtes pour ces liquides Bi,03-B,O,.

Mots elks : thermochimie, calorimttrie, tempkrature ClevCe, oxyde fondu.

[Traduit par la rCdaction]

Introduction
he determination of the enthalpic quantities corresponding to the formation of solid c o m ~ o u ~and , ~ s liquid Or solid tions, is the aim of calorimetry. For oxide systems, within the temperature range where measurements may be done (typitally up to 1700 K), direct reaction between the reactants is always difficult and often even impossible due to the low reaction rates (slow diffusion processes of the elements, slow interface reactions or high viscosities). As a result, for such studies, solution calorimetry, which consists in comparing the destmction energies of the networks of products and reagents, has idly become indispensable where the choice of solvent is difficult. ~ r o m very early stage the curiosity of scientists has been a attracted to dissolution phenomena. In alchemic tradition all the liquids that dissolve certain solids were called "menstrui." The origin of this word stems from the revolution period of the moon, and refers to the generally long duration of this process. In the seventeenth century the chemist Boerhaave defined a "menstruum" as a substance that, "if it were applied to another, following the rules of the art, would break it so finely that the particles the solvent completely with those of the solute" (1). In oxide solution calorimetry, the original idea was to perform the dissolution in the temperature range where the calorimetric experiments are the easiest and also the most accurate, i.e., around ambiant temperature. For a recent example see ref. 2. Acidic and basic aqueous solvents are commonly used. An important drawback to this method is the generally great difReceived June 6, 1994. Revision received December 14, 1994.

ference between the measured thermal effects of the dissolution reactions and the expected enthalpy, which can be some percentage of the former. Moreover, the enthalpy of the reaction of formation is calculated from at least two different S O ~ U further increases the inaccuracy. tion reactions, To overcome this difficulty, it was proposed to use a solvent the chemical nature of which is quite similar to that of the solute, even if the experimental setup imposes a ticklish problem. ~h~ final expected enthalpy and the dissolution energy should be of about the same magnitude. one the main constraints of of this choice is the need to carry out the measurements at high temperature. The studies are generally performed between 500 and 1200 K in a fluxmeter. Nevertheless, these two measurement methods complement one another well. BY means of thermodynamic cycles it is possible to verify the agreement between the measured and estimated quantities such as heat capacities and, in particular, the melting and transition enthalpies, During the last 20 years, only a few groups of researchers have ventured and persevered in the difficult technology of high-temperature solutioncalorimetry in molten oxide melts. The aim has very often been the study of compoun~s geeof logical interest. 0.J. Kleppa and co-workers at the University of Chicago were the pioneers in this technique (3). Later, A. Navrotsky at Princeton University and two groups in Grenoble (France) and in Moscow (CEI) used this method. Such equipment has already enabled the authors to perform thermochemical studies of, for example, the albite-orthoclase and the N~,o-K,o-~~o, (4, 5). systems Various solvents have been investigated by the different groups; in most cases the 2PbO-B,O, melt has been used. The aim of this paper is to propose a new solvent, and the corresponding thermochemical study is presented.

J. ~ o ~ eand J.C. Mathieu. Centre de Thermodynamique et z ' Microcalorimttrie du Centre National de la Recherche Scientifique, 26 rue du 14lkme R.I.A., 13331 Marseille CCdex 3, France.

The choice of a solvent

The choice of a solvent is crucial for successful solution cal0rimetry. This paper is restricted to studies of oxide systems.

'

Author to whom correspondence may be addressed. Telephone: 33-9 1-28-20-50. Fax: 33-9 1-50-38-29.

Can. J. Chem. 73: 425-430 (1995). Printed in Canada 1 ImprimC au Canada

Can. J. Chem. Vol. 7 3 , 1995

The particular conditions the solvent must satisfy have been distinguished from the restricting conditions imposed by the calorimetric setup. (i) The solvent must obviously dissolve the constituents of the systems under consideration. Calorimetric dissolution experiments are long and tedious, and the price to be paid, in time, for a measurement is heavy. For this reason, the chosen melt should be able to dissolve a large number of acid and basic constituents without showing a great difference between the dissolution enthalpies. Thus, the results obtained for various systems can be compared and corroborated. This last condition is satisfied when the solvent presents a buffer character in the sense of the acid-basic reactions in oxide systems as defined by Flood and Forland (6). Generally speaking, the main problem of the experimental investigations is the reproducibility of the measurements. In oxide solution calorimetry it often amounts to a few percent, for example, 4% for SiO, in the 2PbO-B203 melt at 970 K (7). In some cases it may be worse, as stated by Shearer and Kleppa for the dissolution of MgO in 2PbO-B203 (220%) (8). We have also observed such a discrepancy in a previous study of the MgO-Cr,03 system by solution calorimetry in the same solvent. The choice of solvent is always a compromise between fast dissolution kinetics, which induces the use of a strong reagent, and a measured energy that is not too high. In aqueous solvents this dilemma is neatly solved by varying the solvent concentration. The vapor pressure of the solvent must remain very low within the temperature range investigated. During the runs the quantity of solvent must not significantly change and, in the case of a multicomponent melt, the composition must not vary by differential vaporization. From this viewpoint, those simple oxides whose melting points are very low, such as OsO,, Re20,, or, to a lesser degree, TeO,, are not suitable. In most cases the sample is thermally stabilized above the melt surface before the dissolution. If the equilibrium pressure above the melt is too high, the sample may react with the solvent vapor before the expected dissolution in the liquid state. The solvent must present a low viscosity in order to keep the dissolution rate relatively high. Pure boron oxide, for example, has too high a viscosity at 1070 K. The stirring that is necessary in most cases must be mechanically possible without damaging the stirring setup. If the basic constituent is a network former melt, the other constituents have to include some network modifiers in order to diminish the viscosity, which depends on the degree of polymerization. The solvent is commonly prepared outside the calorimeter by melting the various oxides or by thermal decomposition of the corresponding carbonates. Toxicity is then a significant factor in the choice of solvent. Some oxides, such as B,03, Sb203,Moo3, and Bi,O, are not known as toxic reagents. The cations or the metallic atoms of other oxides are toxic after ingestion or inhalation (As203, V205, PbO, with cumulative effect). In this sense the handling of the solvent must be easy. A melt that is insensitive to moisture is more suitable for extended storage. Generally, the enthalpies of formation or the enthalpies of transition are deduced from the partial dissolution enthalpies at infinite dilution. Extrapolation to zero concentration is easier the less the dissolution enthalpy varies with composition. Indeed, a linear dependence with a low or zero slope has been observed in many systems. Though perfect chemical homoge-

Table 1. The melting temperatures Tf (in K) of simple oxides whose melting points are less than 1400 K (10-12).
Chemical formula oso, Re,O, As203 B203 TeOz Sb2 0 3
"20,

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Moo, Biz03 PbO GeO,

neitv in the licluid is sometimes difficult to obtain when. for example, partial crystallizations or vitrifications inducing chemical segregations occur during the quench; the values are generally not sensitive to small concentration differences between batches coming from the same primary melt. Most of these conditions are satisfied when the solvent presents some buffer properties with respect to the acid and basic oxides. A discussion of this point has been already given by Kleppa (9). The choice of PbO-B203 as solvent has been mainly justified by the low variation of the partial enthalpy in the composition range xpb0 = 0.45 to xpbO= 0.8. In addition, the phase diagram presents a wide liquid zone around the eutectic composition close to the compound 2Pb0.B203. When a new solvent is selected this characteristic should be a criterion in the choice of the best com~osition. (ii) The calorimetric configuration imposes some conditions on the choice of solvent. The melting point must be sufficiently low to be within the temperature range of the calorimeters, which generally offer a maximum temperature of about 1300 K. At higher temperature technological problems appear in the mechanical behaviour of the setup. As shown in Table 1 very few single oxides are convenient. Polyconstituent oxides, which present lower melting points as eutectics, are more suitable. It can be mentioned that in oxide systems very low euctectics are not common and most systems show binary or ternary high-meltingpoint compounds. At present, the greatest number of dissolution experiments with various solvents have been performed between 950 and 1250 K. The solvent must not interact with the measurement cell atmosphere, which is generally air. The chosen oxide or mixture of oxides will then be stable under a 0.21 atm partial pressure of oxygen (1 atm = 101.3 kPa). Another important consideration is the reactivity of the solvent with respect to the material constituting the crucible and the stirring equipment. For good heat transfer to the fluxmeter, a metallic crucible having high thermal conductivity is necessary. Pure gold and silver, which are oxide melt resistant, are generally chosen. The dissolution time is important as the metal of the crucible may be exposed to attack-of the solvent for long periods. The kinetics of this dissolution reaction must remain very slow. Even if the dissolution rate is low, mechan-

Rogez and Mathieu ical damage may occur. For example, during local remelting for strengthening some parts of a platinum crucible, some bubbles of alkaline metal or oxide were observed on the crucible walls, which had been previously exposed to NaB0,-LiBO, solvent. The presence of lithium in the melt inay induce a diffusion of this-alkaline element into the grain boundaries of the metal and may then cause it to becomebrittle. The break may occur during further handling of the crucible at ambiant temperature when renewing the solvent between two dissolutions. Diffusion into the grain may also occur if the solubility of the foreign element in the crucible metal is high enough. Tin with respect to platinum is a good example of this phenomenon. If a compound is formed, the diffusion process can be stopped. If the melting point of the corresponding compound is quite near the dissolution temperature, the brittleness at high temperature may increase. Our experience gives a lifetime for platinum crucibles of about 50 runs in 2PbO-B,O, melt and 10 runs in NaB02-LiB0, melt. Finally, the cost of the crucible, which is mainly a labour cost even for precious metals, must be taken into account. The kinetics of the dissolution reaction must be fast compared to the characteristic time for stability of the calorimeter. Typically, the dissolution time should not be greater than 1 h. This rate depends greatiy on transport phenomena in the liquid state, interface reactions during the dissolution being generally rapid. The liquidus slope of the solute-solvent phase diagram gives an indication of the dissolution rate. Thus, most experiments are performed by stirring in the melt, which homogenizes the liquid and also increases the dissolution rate. This kind of setup imposes a measurement of the stirring energy by performing a blank run after each dissolution; this then doubles the experimental time. In conclusion, it seems that pure oxides cannot satisfy these constraints. The solution lies in multicomponent melts including acidic and basic oxides. Because of the toxicity of PbO a new solvent was sought. Solvents based on B,O, are good candidates, as boron oxide is the lowest meltini oxide that satisfies the criteria of toxicity, vapor pressure, and cost. Alkaline earth - boron oxide melts present too high vapor pressures. The alkaline earth - boron oxide svstems show ~ h a s e semrations in the liquid phases and the eutectics are very close to those of the pure oxides. Finally, bismuth oxide - boron oxide melts were selected; as the Bi20,-B20, and PbO-B,03 phase diagrams are similar, it may be expected that the two melts behave similarly. In the following, the thermodynamic study of the Bi2O3-B,O, melt is presented.
-

trolled. At the beginning of the reaction, the temperature is raised slowly in order to control the thermal decomposition of the boric acid. As a final stage of the process, the melt is kept at 1123 K during 1 h. After quenching on a stainless steel plate, the ground solid is melted again at the same final temperature for homogenization.

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Measurements of the partial mixing enthalpies The starting materials for the solute samples are anhydrous boron trioxide provided by Merck (Pro Analysi quality) and the same bismuth(II1) oxide as that used for the solvent. As mentioned in Table 2, about 0.08 mole of solvent is used for each melt composition. The calorimetric measurements are performed in a twin Tian-Calvet-type calorimeter at 1023 K in air. The experimental high-temperature equipment has been described previously (4). The inner diameter of the heat flux sensor is 17 mm and the pure platinum crucible as 70 mm in height and 14 mm in inner diameter. Before dissolution the ground sample (typically < l o 0 km) is thermally equilibrated on a platinum cup just above the free surface of the melt inside the calorimetric cell. Hence, the solute and the solvent are at the same temperature before the reaction. Dissolution begins when the cup is introduced into the liquid by a vertical motion of the calorimetric equipment. Automatic vertical shaking of the cup increases the global dissolution rate. Thermal effects due to the transfer of the cup into the measurement cell and the stirring motion are measured just after completion of the reaction by carrying out the same experiment without a sample. The reproducibility of this blank run is about 95%; it represents about 20% of the overall thermal effect. The thermogram is automatically integrated by a microcomputer. Results In Table 2 and Fig. 1 the partial mixing enthalpies of BiZO, and B20, referred to solid Bi203and liquid B,O, are reported for the various concentrations. The inaccuracy is about 2 4 kJ mol-I except for xn,o, = 0.2 where the discrepancy between the Bi203partial enthalpies is higher. The partial enthalpies do not vary within the error margin in the solute composition ranges 0 < y6i707< 0.004 and 0 < y6?03< 0.0 11. It may then be expected that these values represenithe partial mixing enthalpies. For the B203-rich composition only one value is available because of the too-high viscosity of the melt and the close proximity of this concentration to the phase separation curve in the liquid state, which induces a lower dissolution rate. In only one run did the molten sample not remain stacked in the cup without dissolution. The curves in Fig. 1 fit the results, taking into account the Gibbs-Duhem relation. The integrating pole is Xg,03 = 0.4, AHB203 -48.7 kJ mol-I. The Bi20, partial enthalpy at x = 0 = corresponds to the melting enthalpy given by Robie et al. (10); AH, = 16.74 kJ mol-' . In the concentration range 0.2 < .XB,O, < 0.75 the partial enthalpies do not vary significantly. Consequently this behaviour induces a flat curve for the integral mixing enthalpy referred to the two liquids at around -45 kJ mol-'. After each run and for each melt composition, the resulting liquid was quenched on a stainless steel plate. Because of the heterogeneity of the sample temperature, the mean cooling rate can be estimated at 10 K s-I in the liquidus temperature

Physicochemical study of the system Bi203-B203at 1023 K

The thermochemical properties of the Bi203(,-,)-B203, system in the liquid state have been investigated in the composition range 0.1 < x < 0.8.

Preparation of the solvent 'The starting materials are Extra Pure bismuth(II1) oxide and Pro Analysi boric acid as provided by Merck. For each composition, about 80 g of solvent are prepared by reacting boric acid with bismuth oxide in a platinum crucible. The two weighed powders are carefully mixed and introduced into an open-air furnace whose temperature is electronically con-

Can. J . Chem. Vol. 73, 1995

Table 2. Partial mixing enthalpies of BizO3and Bz03in Bz03-BizO, melts at per 1023 K. The quantities NB,o, or NBi,O, pmol represent the amounts of solute

dissolved in each run. ~ h e - ~ u a n ; t per mmol of the solvent is reported for each tl ~ i ! bath. N ~ i , ~ , l ~ m O 1'n,ixH~i:o, (kJ 47 39 47 -8.82 -5.29 -3.63
mol-l)

N~20,1pmol 193 187 140

Am,xHB?03

(kJ

rnol-l)

0.1 B203 - 0.9 Bi203 (N,lmmol = 64.5)

-

105.0 -104.8 -100.1

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range. For the composition X g 2 0 3 = 0.1 the solid phase is a dark crystal without an apparent glassy phase. At x = 0.2 and 0.4, quenching results in a mixture of a glass with crystals (dark for 0.2 and yellow for 0.4). For X g 7 0 3 = 0.6-0.8 a yellow-orange glass without a crystalline phase was always observed. An Xray analysis was performed on the x = 0.1-0.2-0.4 crystalline phases. The two former samples include the cr Bi203 and the 2Bi20,.B,03 compounds. At x = 0.2 the percentage of this compound is more important than in the x = 0.1 sample. The presence of the 12Bi2O3.B2O,compound cannot be ensured in the x = 0.2 crystalline phase. This latter compound is not observed in the x = 0.4 sample, which contains only the 2Bi203.B203 compound.

Discussion
A comparison between the physicochemical properties of the liquids Bi20,-B20, and PbO-B20, is attempted. First, the liquid PbO-Bi20, is stable enough to form an eutectic whose melting point is 190 K lower than the lowest - . melting point of the constituent oxides (TtBi701 1098 K; = T , = 1 159 K). In the solid state the respectivesolubilities are weak. However, the existence of a large intermediate hightemperature h.c.c. solid solution indicates that the two elements are compatible with oxygen in a single lattice (13). Considering the various solid bismuth and lead oxides, it appears that these elements differ in the possible valence states. Assuming that oxygen adopts in all cases the -2 valency, Pb may present the 2, 813, 3, and 4 valencies and Bi

the 2, 3, and 5. Comparison of the thermodynamic properties of these compounds shows that the more stable oxides (from 900 K to higher temperatures) are PbO (valency +2) and Bi,O, (valency +3). All the other Bi oxides decompose at low temperature and sometimes before the hypothetic melting points. These two valence states may be considered to be the only ones present in the liquid. If the melting point is an indication of the stability of a compound, PbO and Bi203resemble each other closely. A greater similarity is found between the Bi203-B20, and PbO-B20, phase diagrams if the lead oxide is written as Pb202.In the two systems a wide liquid domain is observed at 1000 K, which indicates a greater stability of these phases. The minima of the integral mixing enthalpies are -47 kJ mol-' in the Bi20,-B20, system and -26 kJ mol-' for the PbO-B,03 melt. These values indicate a higher stability of the In former I~quid. the Pb,02-B20, system the minimum of the liquidus is about 750 K as compared to 900 K in the other system. In both cases a phase separation in the liquid state is observed on the boron-rich side. Designating the aBi2O3:bB2O3 and aPb,02:bB,03 solid compounds by a:bBiand n:bpb, the 1:4 and 2: 1 ratios are common to both systems. Corresponding to the 3:5,, composition, three lead compounds that melt peritectically are mentioned (5:8,,, 9:16,,, and 1:16pb).The phase diagrams differ with respect to the 3:5,,, 12: l B i ,and the 1:lPb,which have no corresponding 3:5pb, 12: I,,, and 1: lBi.Among these three compounds only the 3:5,, melts congruently. Assuming a partial ionic decomposition of the corresponding melts, the borate

Rogez and Mathieu

Fig. 1. Integral and partial mixing enthalpies in the B,O,Bi,O, liquid system at 1023 K referred to liquid B,O3 and solid Bi,O,. Dotted lines: partial mixing enthalpies; a:AmixHBi203; A: AmixHB,03. Solid line: integral mixing enthalpy.

Table 3. Possible ionic decompositions of some solid compounds

(Bi,03 or Pb,0,),(B20,), Pb20,-B,03. n:b Bi,O,-B20, written n:b, in systems Bi20,-B,O, and

system

Pb202-B2O3 system

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entities corresponding to these particular compositions may be expected in the presence of three-coordinated boron. Table 3 ' shows that the linear borate anions may be ( ~ ~ 0 , ) -or (B,O,0-B,o,)+, which present a double oxygen-boron bonding (-B=O) at each end of the chains; B0,-, which presents only one -B=O entity; and (B,o,)~, which has no double bonding between B and 0 . The more acid the melt, the more probable are anions with a double bond. Such behaviour has been observed in silicate melts where the following reaction is favoured by an increase in temperature, i.e., when the acidity of melt also increases: (s~,o,)-'
= (Si0,)-'

+ SiO,

In the two systems studied it is necessary to call upon cationic entities such as (P~,o)+', ( ~ i , o , ) + j ,( B ~ , o ~ ) + ~(BiO)' in the or , basic composition range. It appears in this scheme that the polymerization of the cation arises in the Bi203-B203system at a greater boron concentration than in the P~O-B,O, system. As an acid-base function can be defined with respect to the proton in the aqueous milieu, in molten oxide chemistry an acid will be any compound containing one or several particles able to accept an oxygen anion. The basic reaction can be written as (6):
base = acid

+ 0-'

The basicity of a melt is measured via the oxygen activity in the liquid or the value of the constant of the former equilibrium. An oxide is all the more acidic the weaker its'dissocia-

tion and the lower the oxygen anion concentration in the melt. The corresponding element is then all the more electronegative. As the temperature rises the acidity of the melt increases. For example, Si0, behaves as an acid at 1300 K but decomposes as a basic compound into Si+, and 20-' at higher temperature. An amphoteric oxide is a compound that is able either to give or to retain an oxygen anion. Lead oxide is a moderately strong base, as ~ b "is a weak acid. Boron oxide acts as a strong acid. On the electronegativity scale 0 is at 3.5 whereas B is at 2.0, Bi is at 1.9 and Pb at 1.8 (14). It can be assumed that boron oxide and bismuth oxide present about the same acidity and the acid-base behaviour in the Bi203-B203system will be different from that in the PbOB,0, system. The Bi-0 bonding will probably present a less ionic character than that of Pb-0, and will approach the nature of the B-0 bonding. The integral and partial mixing Gibbs free energies corresponding to such an acid-base melt will show some particularities. The Darken function will exhibit some maxima at compositions corresponding to stable entities in the melt (15). In other words, a sharp dependence of the partial thermodynamic functions upon composition will be observed around these particular concentrations. In the present case and to a first approximation, the partial mixing enthalpies will determine the most probable acidic or basic entities that take part in the acid-base reaction of the two oxides. In the concentration regions where the acidity does not vary significantly, the par- : tial thermodynamic function will exhibit a plateau. The solution will then show a buffer character. Such an analysis was performed by Holm and Kleppa on the previously measured partial mixing enthalpies in PbO-B,O, melts (16). Some sharp variations of these thermodynamic functions are observed around the compositions Xp,,o, = 0.160.2 and X B , ~=~0.55-0.6. Assuming that lead is in the ~ b + , state, these concentrations correspond to oxygenhoron ratios of 4-3.5 and of 1.91-1.83, respectively. The authors attribute these anomalies to the appearance of some borate anions: BO,-,, ~ ~ 0corresponding to the same OIB ratios 4-3.5, 7' (OIB = 1.88). These sugand (B,o,,)-6 or (B,o,-o-B,o,)-~ gestions are founded on the possible bonding of boron and oxygen atoms in borate glasses. A buffer region lies between these two concentrations. In the Bi20,-B,0, liquid, such anomalies are observed at Xp,?03 = 0.05-0.15 (OIB = 10-30) and Xp,,o, = 0.75-0.85 (OIB = i.77-2). The buffer conditions are realized for 0.4 < Xp,+ < 0.6. As in the PbO-B,O, melt, the OIB = 1.77-2 ratio may be

430

Can. J . Chern. Vol. 73, 1995

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attributed to the formation of borate anions (B,0,J4 or (B,o,-O-B,O,)~. This assumption is confirmed by thk great stability of the solid compound 1:4Bi(O/B = 1.88; T,= 988 K). For the former entity the high O/B ratio cannot be explained with only a boron-polymerized anion. At this concentration oxygen-bismuth cations are formed. From analyses of the crystalline phases of the quenching products, it may be thought that, as in the 12: 1 ,i compound, and some Bi,03, (BiO)' or ( B ~ ~ o ~ ) " , (B,o~)-' entities appear in the melt for an O/B ratio of about 10-30. The nature of the cation cannot be described precisely from enthalpic measurements alone but it can be established that oxygen-boron cationic entities are present. From this viewpoint further structural characterizations would be of great interest.

Acknowledgments
We are grateful to R. Depeyre for assistance in the dissolution experiments.

References
1. M. Goupil. Irz Du flou au clair. Histoire de l'affinite chimique. ~ d i t i o n Cornit6 des Travaux Historiques et du Scientifiques, Paris. 1991. p. 99. 2. M. Ganteaume, M. Coten, and M. Decressac. Thermochim. Acta, 178, 8 1 (1991). 3. T. Yokokawa and O.J. Kleppa. J. Inorg. Chem. 5-7,954 (1964). 4. J. Rogez, R. Chastel, C. Bergman, C. Brousse, R. Castanet, and J.C. Mathieu. Bull. Mineral. 106, 119 (1983). 5. J. Rogez and J.C. Mathieu. Phys. Chem. Liq. 3-7, 954 (1985). 6. H. Flood and T. Forland. Acta Chemica Scand. 1, 592 (1947). 7. R.C. Newton, T.V. Charlu, and O.J. Kleppa. Geochim. Cosmochim. Acta, 44,933 (1980). 8. J.A. Shearer and O.J. Kleppa. J. Inorg. Nucl. Chem. 35, 1073 (1973). 9. O.J. Kleppa. NATO Adv. Study Inst. Proc. Newcastle, England. 1974. pp. 369-387. 10. L.B. Pankratz, J.M. Stuve, and N.A. Gokcen. Thermodynamic data for mineral technology. Bureau of Mines, Bulletin 677. 1984. 11. R.A. Robie, B.S. Hemingway, and J.R. Fisher. Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar pressure and at higher temperatures. Geological Survey Bulletin 1452, U.S. Government Printing Office, Washington. 1978. 12. R.C. Weast (Editor-). Handbook of chemistry and physics. CRC Press, Boca Raton, Fla. 1984. 13. E.M. Levin, C.R. Robbins, and H.F. McMurdie. Phase diagrams for ceramists. Vol. I. Edited by M.K. Reser. The American Ceramic Society, Ohio. 1964. pp. 115, 125, 126. 14. A.N. Bloch and G.C. Schatteman. In Structure and bonding in crystals. Vol. 1. Edited by M. O'Keeffe and A. Navrotsky. Academic Press, New York. 198 1. p. 58. 15. L.S. Darken. Trans. Metall. Soc. AIME, 239, 80 (1967). 16. J.L. Holm and O.J. Kleppa. Inorg. Chem. 6-4, 645 (1967). 17. P. Richet, R.A. Robie, J. Rogez, B.S. Hemingway, P. Courtial, and C. Tequi. Phys. Chem. Miner. 17, 385 (1990). 18. F.A. Shunk. Constitution of binary alloys. 2nd suppl. McGraw-Hill Book Company, New York. 1969.

Bi203(, -,,-B203,

melts as solvents

I
I

To verify the ability of these melts to dissolve various solutes, dissolutions of simple oxides such as SiO, in the quartz and glassy form, and of Cr,03, MgO, FeO, and some glassy melts of MgO-SiO, have been carried out in the 8Bi,032B203melt at 923 K. The dissolution enthalpies lie between 0 and -40 kJ mol-'. No significant variations as a function of solute concentration in the melt were observed. These dissolution enthalpies remain in all cases about 20-30 kJ mol-I lower than those obtained in 2Pb0-B,03. The thermodynamic study of the carnegieite crystal -glassy nepheline transition in 4Bi,03-6B,03 liquid was successfully performed at 1023 K (17). All the experiments were carried out in a platinum crucible of 0.3 mm thickness. No chemical attack or weight variations were observed during the runs. For the composition richest in B,03 the diameter of the crucible became larger during the cooling, producing some mechanical damage. Such phenomena were not observed for lower X.B~O, contents. For experiments of long duration, a diffusion of Bi in the crucible metal may occur. On the platinum-rich side of the Bi-Pt phase diagram a eutectic at 1003 K is mentioned, between the pure Pt and the Bi:Pt compound whose melting point is 1038 K (18). For previously mentioned reasons, experiments of long duration at temperatures higher than 1000 K will perhaps be difficult. < It seems that for 0.4 < X B , , ~ ~0.6 the buffer conditions are realized. Considering the dissolution experiments, it appears that the viscosities of the PbO-B203 and Bi20,-B20, melts are very similar. Although indications regarding the toxicity of chemicals are very scarce, it has been established that the Bi compounds are less toxic than the Pb compounds. Form these remarks it can be concluded that Bi,O,-B203 melts are good solvents for oxide melt solution calorimetry.

,,,,