Thermochemistry of the high structural state plagioclases

The enthalpies of solution of a suite of 19 high-structural state synthetic plagioclases were measured in a Pb₂B₂O₅ melt at 970 K. The samples were crystallized from analyzed glasses at 1200°C and 20 kbar pressure in a piston-cylinder apparatus. A number of runs were also made on Amelia albite and Amelia albite synthetically disordered at 1050–1080°C and one bar for one month and at 1200°C and 20 kbar for 10 hr. The component oxides of anorthite, CaO, Al₂O₃ and SiO₂, were remeasured.The ΔH of disorder of albite inferred in the present study from albite crystallized from glass is 3.23 kcal, which agrees with the 3.4 found by Holm and Kleppa (1968). It is not certain whether this value includes the ΔH of a reversible displacive transition to monoclinic symmetry, as suggested by Helgesonet al. (1978) for the Holm-Kleppa results. The enthalpy of solution value for albite accepted for the solid solution series is based on the heat-treated Amelia albite and is 2.86 kcal less than for untreated Amelia albite.The enthalpy of formation from the oxides at 970 K of synthetic anorthite is ?24.06 ± 0.31 kcal, significantly higher than the ?23.16 kcal found by Charluet al. (1978), and in good agreement with the value of ?23.89 ± 0.82 given by Robieet al. (1979), based on acid calorimetry.The excess enthalpy of mixing in high plagioclase can be represented by the expression, valid at 970 K: ΔH^ex(±0.16 kcal) = 6.7461 X_abX²_An + 2.0247 X_AnX²_Ab where X_Ab and X_An are, respectively, the mole fractions of NaAlSi₃O₈ and CaAl₂Si₂O₈. This ΔH^ex, together with the mixing entropy of Kerrick and Darken's (1975) Al-avoidance model, reproduces almost perfectly the free energy of mixing found by Orville (1972) in aqueous cation-exchange experiments at 700°C. It is likely that Al-avoidance is the significant stabilizing factor in the high plagioclase series, at least for X_An≥ 0.3. At high temperatures the plagioclases have nearly the free energies of ideal one-site solid solutions. The Al-avoidance model leads to the following Gibbs energy of mixing for the high plagioclase series: $\text{ΔG}{}^{\mathrm{mix}}\text{= ΔH}{}^{\mathrm{ex}}\text{+ RT X}{}_{\mathrm{Ab}}\text{ln[X}{}^2{}_{\mathrm{Ab}}\text{(2 ? X}{}_{\mathrm{Ab}}\text{)]+ X}{}_{\mathrm{An}}\text{ln}\text{[X}{}_{\mathrm{An}}\text{(1+X}{}_{\mathrm{An}}\text{)}{}^2\text{]}\text{4}$. The entropy and enthalpy of mixing should be very nearly independent of temperature because of the unlikelihood of excess heat capacity in the albite-anorthite join.     

Enthalpy effects associated with Al/Si ordering in anhydrous Mg-cordierite

Measurements of the heats of solution (ΔH_soln) in molten Pb₂B₂O₅ at 708°C of anhydrous magnesian cordierites, prepared with a range of structural states, show that the enthalpy effect associated with Al/Si ordering is substantial (? 9.76 ± 1.56 kcal mole^?1). Differences in the state of order between synthetic cordierites used in phase equilibrium studies and cordierites in the natural environment could lead to significant errors in the estimation of palaeo-pressures and temperatures. A continuous change of ΔH_soln with annealing time supports the suggestion of putnis (1980) that the hexagonal → orthorhombic transformation in cordierite, which can occur via a modulated structure, is truly continuous under metastable conditions. In addition, a linear relation between ΔH_soln and the logarithm of annealing time has been found, which provides some insight into the nature of the ordering mechanisms at an atomic level. Al and Si exchanges occur continuously between neighbouring tetrahedral sites with a net drift towards increasing order. No kinetic or thermochemical distinction can be made between the development of long range and short range order.The enthalpy of vitrification (~ 12 kcal mole^?1) for a metastable stuffed β-quartz polymorph of cordierite composition is similar to that for pure quartz (on a per two oxygen basis), while the heat of vitrification for even the most disordered cordierite seen in this study is more than a factor of three greater (~40 kcal mole^?1). This is consistent with the view that cordierite glass resembles the quartz structure more closely than the crystalline cordierite structure, and that crystallisation of the glass below ~900°C is controlled by a tetrahedral framework.     

The effect of water,pressure, and strain on Al/Si order-disorder kinetics in feldspar

The disordering kinetics of Al/Si in albite depend on how the samples are dried, and thus on the presence of trace amounts of water. The disordering rate increases with water content and confining pressure. At 10 kb the activation energy is about 67 kcal/mole compared to about 87 kcal/mole for samples disordered in air. Simultaneous plastic deformation increases the disordering rate and the effect is most pronounced below 900° C at 10^?6/s. Some albite ordering and microcline disordering experiments show similar kinetic behavior. These results are significant for interpreting the structural state and the high-temperature deformation of feldspars.     

Sillimanite—disordering enthalpy by calorimetry

Heat of solution measurements in an oxide-melt were performed on samples of natural sillimanite heat-treated in the range 1200–1700°C at pressures of 16–23 kbar. A distinct enthalpy of solution decrement relative to the unheated sillimanite of about 1.3 kc/mole is shown by samples run at 1400–1550°C. Pressure variations in the range 16–23 kbar cause little change in the heat of solution in this temperature range. This pressure-independent ‘plateau’ in heat of solution is interpreted to be due to Al-Si disordering on tetrahedral sites in the sillimanite structure. A simple temperature-dependent disordering model developed by navrotsky and Kleppa (1967) for spinels leads to an Al-Si interchange enthalpy, Δ_Hnt, of16 ± 1 kcal/mole, in good agreement with the value derived by Holdaway(1971) on entirely different grounds.Above 1550°C, larger heat of solution decrements were observed. Microprobe analyses of quenched samples indicate that the sillimanite has not deviated significantly from the ideal formula. Some unknown profound disordering process may account for the heat effects in the very high temperature range.Unit cell volumes of quenched samples also describe a ‘plateau’ region in the temperature range 1400–1550°C. This plateau consists of an increase of the 6 crystallographic axis beginning at 1350°C without much change in the other axes in the range 1350–1550°C. A sudden expansion of the α-axis occurs between 1550 and 1630°C.We conclude that Al-Si disorder of the type postulated by Beger et al. (1970), and Holdaway (1971) has been confirmed calorimetrically for samples heated under pressure in the temperature range 1400–1550°C.     

Kinetics of intracrystalline order-disorder reactions in tremolite

The temperature dependent Fe-Mg distribution in tremolite from Zillertal, Austria was investigated using Mössbauer spectroscopy. The standard free energy change for the exchange reaction Fe²⁺(M4)+Mg(M2)=Mg(M4)+Fe²⁺(M2) decreases with increasing temperature, corresponding to an enthalpy term of 9.2±1.5 kcal/mole and an entropy term of 1.9±1.7 cal/mole K. Kinetic experiments performed as hydrothermal runs, yield an activation energy of 70±7 kcal/mole for the disordering reaction. Difficulties in analysing the very small amount of Mg(M4) in the natural sample introduce large errors in the calculation of cooling rates for the natural rock. The estimated error in the Mg(M4) site occupancy results in a shift of the obtained cooling rate of about three orders of magnitude, making tremolite less useful for estimations of rock cooling rates.     

Laboratory simulation of meteoritic noble gases. I. Sorption of xenon on carbon: Trapping experiments

We have studied trapping of radioactive ¹²⁷Xe in three types of carbon: carbon black (lamp black  LB), pyrolyzed polyvinylidene chloride (PVDC), and pyrolyzed acridine (C₁₃H₉N). A total of 86 samples were exposed to Xe at T between 100 and 1000°C, for times between 5 min and 240 hours, at p_xe ~ 5 × 10^?7 atm. Excess gas phase and loosely sorbed Xe were pumped away and the remaining, tightly bound Xe was measured by γ-spectrometry.At 100°C,× >90% of the Xe desorbs within a few minutes' pumping but a small amount remains even after 4000 min. Distribution coefficients for this tightly bound Xe are ~1 × 10^?2, 1 and 10 ccSTP/g atm for LB, acridine and PVDC carbons. The tightly bound Xe consists of two components. One occurs over the entire range 100–1000°C, becoming less abundant at high T; it appears to be physisorbed. The other occurs only at T > 500°C and is probably due to volume diffusion. The adsorbed component in LB has an apparent ΔH between ?2.3 and ?5.7 kcal/mole. The diffused component, which occurs in LB and possibly in acridine carbon, has an activation energy Q = 27 ± 8 kcal/mole and a diffusion coefficient D = 1.3 × 10^?17 cm²/sec at 1000°C. These values are comparable to those found for other types of amorphous carbon (Morrisonet al., 1963; Nakai et al., 1960).The low-T component displays two paradoxical features: low ΔH_ads, in the range for Xe physisorbed on carbon, but exceedingly long adsorption or desorption times (~10³ min at 100–400 or 1000°C). Although these long times seem to suggest a high energy process such as chemisorption, our results are best explained by a model that invokes physisorption within a labyrinth of micropores—of atomic dimensions—known to exist in amorphous carbons. The long adsorption/desorption times reflect either the long distances (~5 cm) Xe atoms must migrate by random walk to enter or leave the labyrinth, or the long times needed for Xe atoms to traverse tight spots or constricted pores that connect interior and exterior surfaces of the carbon (activated entry). Both variants of this model predict long equilibration times for the observed ΔH_ads of ?2 to ?6 kcal/mole. Apparently, xenon can be tightly trapped in carbon without resorting to high-energy bonding or to exotic mechanisms.These results suggest that “planetary” type noble gases in meteorites, located at or near grain surfaces of amorphous carbon, may be trapped by adsorption in micropores, whereas components such as CCFXe, which are uniformly distributed in their carrier phases, may be trapped by mechanisms such as volume diffusion or ion implantation.     

Thermochemistry of some pyroxenes and related compounds

The enthalpies of formation of a number of crystalline silicates from the oxides at 986 K were determined by oxide melt solution calorimetry. The values of ΔH°_{f, 986}, in kcal/mol, are as follows: MgCaSi₂O₆, ? 34.3 ± 0.4; CoCaSi₂O₆, ? 26.7 ± 0.5; NiCaSi₂O₆, ? 27.1 ± 0.5; MnSiO₃, ? 6.3 ± 0.3; Mn₂SiO₄, ? 12.2 ± 0.3. In addition, for MnSiO₃ (rhodonite)→ MnSiO₃ (pyroxmangite), ΔH°₉₈₆ = + 0.06 ± 0.3₃kcal/mol and for MgCaSi₂O₆ (diopside) = MgCaSi₂O₆ (glass), ΔH°₉₈₆ = + 21.0 ± 0.3 kcal/ mol. For hedenbergite, FeCaSi₂O₆, ΔG°₁₃₅₀ = ?25.6 ± 1.5 kcal/mol. In terms of pyroxene phase equilibria and crystal chemistry, our thermochemical data support the generally accepted crystallographic arguments that (a) the C2/c clinopyroxene structure increases in stability with decreasing size of the ion occupying the Ml site in the MCaSi₂O₆ series, and (b) the energy (and enthalpy) differences between orthopyroxene, clinopyroxene, and pyroxenoid structures are generally quite small and often less than 500 cal/mol in magnitude.     

Structure energies of the alkali feldspars

Structural energetics of the alkali feldspars have been studied using a “lattice” or structure energy model. Electrostatic energies, U _e,for 20 well-refined, non-intergrown alkali feldspars were calculated using Bertaut's (1952) summation procedure and average about ?13,400 kcal/mol; the repulsive energies of the alkali site in each structure (～15 kcal/mol) were calculated using repulsive parameters for K-O and Na-O interactions estimated from bulk modulus data for NaF and KF and the exponential form of the repulsive potential. Using a procedure in which the position of the alkali cation was varied while the oxygen cage was kept fixed, structure energy gradients for the alkali sites of high albite and a hypersolvus Ab₄₂Or₅₈ structure were computed. In both cases, a broad structure energy well, elongated approximately parallel to c and subparallel to the observed split Na positions, was found. In both structures there is a single energy minimum corresponding closely with the observed single alkali positions. Comparison of U _e values for the alkali feldspars with different K/Na ratios shows that intermediate compositions are predicted to be less “stable” than either endmember and that the potassic end-member is predicted to be less “stable” than the sodic one, assuming that all other factors contributiong to the free energies of each phase are approximately the same. Comparison of U _e values for the high albite and low sanidine structures with different Al/Si distributions and a fixed tetrahedral framework indicates that the ordered charge distributions are 63.0 and 54.8 kcal/mol, respectively, more “stable” than the disordered distributions. Smaller, more realistic energy differences were obtained by using U _evalues averaged from four separate calculations with a +3 charge on a different T site in each and with +4 charges on the other T sites. If, in addition, the charges on cations and oxygen are reduced to half their nominal formal charges, in agreement with Pauling's electroneutrality principle and the results of recent molecular orbital calculations on silicates, the predicted electrostatic energy differences are reduced to 3.6 and 1.6 kcal/mol, respectively. These calculations also indicate that the T₁O site in the high albite structure energetically favors Al and that the Al/Si distribution determines the Na position within the alkali site.     

Calorimetric determination of the enthalpy of Mg-Fe ordering in orthopyroxene

The enthalpy of Mg-Fe ordering in En₅₀Fs₅₀ orthopyroxene was measured using the transposed temperature drop calorimetric method. Heat effects associated with two consecutive drops were recorded. In the first drop, synthetic orthopyroxene samples equilibrated at 823?K, 0.1?MPa and a f?O₂ of the WI buffer were dropped from 823?K into the calorimeter, which was held at 1173?K. The measured heat effect corresponds to the enthalpy change due to the heat capacity of the sample from 823 to 1173?K and to the enthalpy associated with the (dis)ordering of Mg and Fe²⁺. In the second drop, the samples, with an Fe-Mg order corresponding to 1173?K, were dropped again from 823 to 1173?K. From the difference of the heat effects measured in the two experiments, the enthalpy of disordering associated with the temperature change from 823 to 1173?K was calculated to be ?1.73±0.04 J mol^?1. The observed enthalpy corresponds to a change in the mole fraction of iron on the M2 site, ΔX _Fe,M2=?0.096 ± 0.001, which leads to of ΔH ⁰ _exch of 18.0 ± 0.4 kJ mol^?1 for the exchange reaction: The degree of Fe-Mg order was characterized by ⁵⁷Fe Mössbauer resonance spectroscopy. In order to minimize the error due to the thickness of the absorber, the iron concentration of the absorber was reduced step by step from 5 to 1 mg?Fe?cm^?2. The iron distribution extrapolated to zero thickness was used for the calculations of the enthalpy of exchange reaction.     

The reaction forsterite+cordierite=aluminous orthopyroxene+spinel in the system MgO-Al2O3-SiO2

Reversal experiments at 1,150–1,300°C on the reaction forsterite+cordierite=aluminous orthopyroxene+spinel in the system MgO-Al₂O₃-SiO₂ show the equilibrium to have a negativedT/dP. The slope andT-P location of this equilibrium have been modelled using available heat capacity data and various structural models which explore the configurational entropy contributions to the totalΔS. The experimental data are consistent with the aluminous orthopyroxene model of Ganguly and Ghose (1979) where limited Al disorder occurs between theM1 andM2 sites, Al-Si mixing occurs on the tetrahedralB site with the ‘aluminum avoidance’ principle maintained, and Mg-Al disorder occurs in spinel with an interchange enthalpy of 9–12 kcal mol^?1. Additionally, Al-Si disordering which occurs in the indialite structure of cordierite is inconsistent with the experimental data and all pyroxene and spinel mixing models; consequently, Si and Al in anhydrous cordierites to 1,300°C in the system MgO-Al₂O₃-SiO₂ must be largely ordered.     

Eight-phase alkali feldspars: low-temperature cryptoperthite, peristerite and multiple replacement reactions in the Klokken intrusion

Eight feldspar phases have been distinguished within individual alkali feldspar primocrysts in laminated syenite members of the layered syenite series of the Klokken intrusion. The processes leading to the formation of the first four phases have been described previously. The feldspars crystallized as homogeneous sodian sanidine and exsolved by spinodal decomposition, between 750 and 600 °C, depending on bulk composition, to give fully coherent, strain-controlled braid cryptoperthites with sub-μm periodicities. Below ~500 °C, in the microcline field, these underwent a process of partial mutual replacement in a deuteric fluid, producing coarse (up to mm scale), turbid, incoherent patch perthites. We here describe exsolution and replacement processes that occurred after patch perthite formation. Both Or- and Ab-rich patches underwent a new phase of coherent exsolution by volume diffusion. Or-rich patches began to exsolve albite lamellae by coherent nucleation in the range 460–340 °C, depending on patch composition, leading to film perthite with ≤1 μm periodicities. Below ~300 °C, misfit dislocation loops formed, which were subsequently enlarged to nanotunnels. Ab-rich patches (bulk composition ~Ab₉₁Or₁An₈), in one sample, exsolved giving peristerite, with one strong modulation with a periodicity of ~17 nm and a pervasive tweed microtexture. The Ab-rich patches formed with metastable disorder below the peristerite solvus and intersected the peristerite conditional spinodal at ~450 °C. This is the first time peristerite has been imaged using TEM within any perthite, and the first time peristerite has been found in a relatively rapidly cooled geological environment. The lamellar periodicities of film perthite and peristerite are consistent with experimentally determined diffusion coefficients and a calculated cooling history of the intrusion. All the preceding textures were in places affected by a phase of replacement correlating with regions of extreme optical turbidity. We term this material ultra porous late feldspar (UPLF). It is composed predominantly of regions of microporous very Or-rich feldspar (mean Ab_2.5Or_97.4An_0.1) associated with very pure porous albite (Ab_97.0Or_1.6An_1.4) implying replacement below 170–90 °C, depending on degree of order. In TEM, UPLF has complex, irregular diffraction contrast similar to that previously associated with low-temperature albitization and diagenetic overgrowths. Replacement by UPLF seems to have been piecemeal in character. Ghost-like textural pseudomorphs of both braid and film parents occur. Formation of patch perthite, film perthite and peristerite occurred 10⁴–10⁵ year after emplacement, but there are no microtextural constraints on the age of UPLF formation.     

The thermodynamic properties of radium

The enthalpy, Gibbs free energy, and entropies of aqueous radium species and radium solids have been evaluated from empirical data, or estimated when necessary for 25°C and 1 bar. Estimates were based on such approaches as extrapolation of the thermodynamic properties of Ca, Sr, and Ba complexes and solids plotted against cationic radii and charge to radius functions, and the use of the Fuoss or electrostatic mathematical models of ion pair formation (Langmuir, 1979). Resultant log K (assoc) and ΔH⁰ (assoc) (kcal/mol) values are: for RaOH⁺ 0.5 and 1.1; RaCl⁺ ?0.10 and 0.50; RaCO⁰₃ 2.5 and 1.07; and RaSO⁰₄ 2.75 and 1.3. Log Ksp and ΔH⁰ (dissoc) (kcal/mol) values for RaCO₃(c) and RaSO₄(c) are ?8.3 and ?2.8, and ?10.26 and ?9.4, respectively.Trace Ra solid solution in salts of Pb and of the lighter alkaline earths, has been appraised based on published distribution coefficient (D) data, where D ～- (mM²⁺)(N_RaX)/(mRa²⁺)(N_MX) (m and N are the aqueous molality and mole fraction of Ra and cation M in salt X, respectively. The empirical solid solution data have been used to derive both enthalpies and Gibbs free energies of solid solution of trace Ra in sulfate and carbonate minerals up to 100°C. Results show that in every case D values decrease with increasing temperature. Among the sulfate and carbonate minerals, D values decrease for the following minerals in the order: anhydrite > celestite > anglesite > barite > aragonite > strontianite > witherite > cerussite.     

Enthalpies and Volumes Related to K--Na Mixing and Al-Si Order/Disorder in Alkali Feldspars

In order to investigate the thermodynamic properties of alkalifeldspars, three new feldspar ion-exchange series have beensynthesized, two based on monoclinic parent materials havingintermediate degrees of Al—Si order, the other on Amelialow albite. Acid solution calorimetric measurements have beencarried out in 20?1% HF at 50?C under isoperibolic conditionson 30 members of the three series, and compared with revisedvalues for a previously reported sanidine—analbite series.Molar volumes have been determined for all feldspars, and foran additional series based on Eifel sanidine. Enthalpies of K—Na mixing (A_ex) calculated from the 50?Cheats of solution are dependent on Al—Si distributionfor both topochemically monoclinic and triclinic alkali feldspars,and in general can be expressed as where N_Or and N_Ab are mole fractions of KAlSi₃O₈ and NaAlSi₃O₈,respectively, and Z is an ordering parameter defined as twicethe difference in the mole fraction of Al in the T1 vs the T2tetrahedral sites. A_ex values for all but the most disorderedseries are maximized toward sodic compositions, and increaseboth in magnitude and asymmetry as ordering increases. For topochemically monoclinic alkali feldspar series, volumesof K—Na mixing(V_ex) are asymmetric with N_Or, but withinthe precision of present data do not depend on Al—Si distribution: Microcline-low albite feldspars appear to have volumes of mixingwith the opposite asymmetry, but expressions of for these differ somewhat among various investigators. Since no single thermodynamic mixing property is markedly asymmetricwith respect to composition, the excess Gibbs energies impliedfrom solvus data for alkali feldspars, and maximized at sodiccompositions, are apparently the result of additive effectsof subtle asymmetries in the volumes, enthalpies, and entropiesof K—Na mixing in these minerals. The thermodynamic properties of an alkali feldspar at any compositionare significantly affected by the distribution of Al and Sibetween T1 and T2 tetrahedral sites. The enthalpy of formationat 50?C of a monoclinic potassium feldspar with perfect order(Z=1) differs by 2?19 kcal/mol from one with a completely randomAl—Si distribution (Z=0), while a value of 2?86 kcal/molapplies to analagous sodium end members. ConverselyY-ordering(between T1O andT1m sites) seems to have little or no effecton the enthalpy of formation of either end member, evidencedby the fact that most of the enthalpy differences for the lowmicrocline to sanidine and corresponding low albite to analbitetransitions (1?73 and 2?79 kcal/mol, respectively) can be attributedto Al—Si exchanges between T1 and T2 sites. Observed enthalpydifferences in alkali feldspars are probably related to strainat domain boundaries, whether the domains are extremely small,or somewhat larger as in modulated structures. Neither Z-nor Y-ordering has a substantial effect on the molarvolumes of alkali feldspars.     

Constraints on the thermodynamic mixing properties of plagioclase feldspars

Taking account of the Cˉ1/Iˉ1 (Al/Si order/disorder) transformation at high temperatures in the albite-anorthite solid solution leads to a simple model for the mixing properties of the high structural state plagioclase feldspars. The disordered (Cˉ1) solid solution can be treated as ideal (constant activity coefficient) and, for anorthite-rich compositions, deviations from ideality can be ascribed to cation ordering. Values of the activity coefficient for anorthite in the Cˉ1 solid solution (γ _An ^Cˉ1 ) are then controlled by the free energy difference between Cˉ1 and Iˉ1 anorthite at the temperature (T) of interest according to the relation: ΔˉG _ord ^Iˉ1 ⇌Cˉ1 =RT ln γ _An ^Cˉ1 . If the Iˉ1⇌Cˉ1 transformation in pure anorthite is treated, to a first approximation, as first order and the enthalpy and entropy of ordering are taken as 3.7±0.6 kcal/mole (extrapolated from calorimetric data) and 1.4–2.2 cal/mole (using an equilibrium order/disorder temperature for An₁₀₀ of 2,000–2,250 K), a crude estimate of γ _An ^Cˉ1 for all temperatures can be made. The activity coefficient of albite in the Cˉ1 solid solution (γ _Ab ^Cˉ1 ) can be taken as 1.0. The possible importance of this model lies in its identification of the principal constraints on the mixing properties rather than in the actual values of γ _An ^Cˉ1 and γ _Ab ^Cˉ1 obtained. In particular it is recognised that γ _An ^Cˉ1 depends critically on ordering in anorthite as well as, at lower temperatures, any ordering in the Cˉ1 solid solution. A brief review of activity-composition data, from published experiments involving ranges of plagioclase compositions and from the combined heats of mixing plus Al-avoidance entropy model (Newton et al. 1980), reveals some inconsistencies. The values of γ _An ^Cˉ1 calculated using the approach of Newton et al. (1980), although consistent with Orville's (1972) ion exchange data, are slightly lower than values derived from experiments by Windom and Boettcher (1976) and Goldsmith (1982) or from ion-exchange experiments of Kotel'nikov et al. (1981). Based on the Cˉ1/Iˉ1 transformation model, values of γ _An ^Cˉ1 <1.0 are unlikely. Discrepancies between the experimental data sets are attributed to incomplete (non-equilibrium) Al/Si order attained during the experiments. It is suggested that the choice of activity coefficients remains somewhat subjective. The development of accurate mixing models would be greatly assisted by better thermodynamic data for ordering in pure anorthite and by more thorough characterisation of the state of order in plagioclase crystals used for phase equilibrium experiments.     

Fluorite solubility equilibria in selected geothermal waters

Calculation of chemical equilibria in 351 hot springs and surface waters from selected geothermal areas in the western United States indicate that the solubility of the mineral fluorite, CaF₂, provides an equilibrium control on dissolved fluoride activity. Waters that are undersaturated have undergone dilution by non-thermal waters as shown by decreased conductivity and temperature values, and only 2% of the samples are supersaturated by more than the expected error. Calculations also demonstrate that simultaneous chemical equilibria between the thermal waters and calcite as well as fluorite minerals exist under a variety of conditions.Testing for fluorite solubility required a critical review of the thermodynamic data for fluorite. By applying multiple regression of a mathematical model to selected published data we have obtained revised estimates of the pK (10,96), ΔG^o_f (?280.08 kcal/mole), ΔH^o_f (?292.59 kcal/mole), S° (16.39 cal/deg/mole) and C^o_P (16.16 cal/deg/mole) for CaF₂ at 25°C and 1 atm. Association constants and reaction enthalpies for fluoride complexes with boron, calcium and iron are included in this review. The excellent agreement between the computer-based activity products and the revised pK suggests that the chemistry of geothermal waters may also be a guide to evaluating mineral solubility data where major discrepancies are evident.     

The stability of CaCO3·6H2O (ikaite)

Experimental runs were made in cold-seal pressure vessels using synthetic CaCO₈·6H₂O, calcite and aragonite as starting materials. The reaction CaCO₃·6H₂O (ikaite) ? CaCO₃ (calcite I) + 6H₂O was reversed across its metastable extension into the aragonite stability field and the phase boundary is defined by brackets at 4.14kb, 14.3°C and 2.96 kb, ?3.0°C. An invariant point for CaCO₃·6H₂O, calcite I, aragonite and water thus occurs at about 3.02 kb and ?2.0°C. No other reaction could be reversed. Calculations based on the equilibrium phase boundary between calcite and ikaite and the available thermochemical data for calcite and water yield the stadard free energy of formation, standard enthalpy of formation and third law entropy of CaCO₃·6H₂O at 25°C and 1 bar total pressure; ?607.3 kcal/mole, ?705.8 kcal/mole, and 88.4 cal/deg mole, respectively.     

Distribution of gold and rhenium between nickel-iron and silicate melts: implications for the abundance of siderophile elements on the Earth and Moon

The distribution equilibrium of Au and Re between nickel-iron and basaltic melts was studied at 1400–1600°C, using radioactive tracers. Metal/silicate distribution coefficients were 1–3 orders of magnitude higher than earlier estimates, as follows. Mauna Loa basalt—Fe₁₀Ni₉₀: D_Au = 3.3 × 10⁴, D_Re = (2.4?89) × 10⁴. Gorda Ridge basalt—Fe₁₀Ni₉₀: D_Au = (18?75) × 10⁴. Synthetic lunar basalt—Fe₇₀ Ni₃₀: D_Au≥ 2 × 10⁴, D_Re ≥ 2 × 10³. The experimental ΔG₁₈₀₀^° for the distribution of Au between nickel-iron and Mauna Loa basalt is ?40 kcal/mole, compared to a calculated value of about ?110 kcal/mole for a reaction involving simple Au³⁺ ions. Presumably the difference represents stabilization of Au(III) by complex formation with ligands such as Cl^?, H₂O, etc.Gold abundances in lunar basalts are roughly consistent with the measured D_Au, but those in terrestrial basalts are two orders of magnitude too high. This discrepancy may reflect complexing by volatiles in the Earth's upper lithosphere, as well as oxidative destruction of metal in the final stages of accretion. In the absence of a metal phase, siderophile trace elements would remain trapped in the upper mantle and crust.     

Thermochemistry of synthetic clinopyroxenes on the join CaMgSi2O6-Mg2Si2O6

Enthalpies of solution of synthetic clinopyroxenes on the join CaMgSi₂O₆-Mg₂Si₂O₆ have been measured in a melt of composition Pb₂B₂O₅ at 970 K. Most of the measurements were made on samples crystallized at 1600°–1700°C and 30 kbar pressure, which covered the range 0–78 mole per cent Mg₂Si₂O₆, and whose X-ray patterns could be satisfactorily indexed on the diopside (C2/c) structure. For the reaction: Mg₂Si₂O₆→-Mg₂Si₂O₆ enstatite diopside the present data, in conjunction with previous and new measurements on Mg₂Si₂O₆ enstatite, determine ΔH° ~ 2 kcal and W_H (regular solution parameter) ~ 7 kcal. These values are in good agreement with those deduced by Saxena and Nehru (1975) from a study of high temperature, high pressure phase equilibrium data under the assumption that the excess entropy of mixing is small, but, in light of the recent theoretical treatment of Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), the meanings of these parameters may be ambiguous.Heat of solution measurements on Ca-rich binary diopsides made by annealing glasses at 1358°C in air gave slighter higher values than the higher temperature high pressure samples. This may be evidence for some (Ca, Mg) disorder of the sort postulated by Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), although no differences in heat of solution dependent on synthesis temperature in the range 1350°–1700°C could be found in stoichiometric CaMgSi₂O₆.     

A thermochemical study of monohydrocalcite

The thermodynamic properties of monohydrocalcite, CaCO₃ · H₂O, have been obtained using a well-characterized natural specimen. Equilibration of the solid with water at 25°C under 0.97 atm CO₂ led to an activity product [Ca²⁺][CO₃^2?] = 10^?7.60±0.03 and a free energy of formation ΔG_f^o = ?325,430 ± 270 calmol^?. The enthalpy of solution of monohydrocalcite in 0.1 N HCl at 25°C led to a standard enthalpy of formation ΔH_f^o = ?358,100 ± 280 cal mol^?1. Estimates of the variation of ΔG_f with temperature and pressure showed monohydrocalcite to be metastable with respect to calcite and aragonite.     

Lead orthophosphates—II. Stability of cholopyromophite at 25°c

The conversion of secondary lead orthophosphate [PbHPO₄] into chloropyromorphite [Pb₅(PO₄)₃Cl] in ca. 10^?1 M NaCl solutions has been investigated at 25°C. From the composition of the supernatant solutions, the solubility product constant for Pb₅(PO₄)₃Cl has been calculated to be 10^?84.4±0.1, corresponding to $\text{ΔG}{}_{\mathrm{?}}\text{°}$ of ?906.2 kcal mol^?1. The solution equilibria and phase relationships in the system PbCl₂-PbO-P₂O₈-H₂O are discussed along with the geological implications.