The effect of added dissolved calcium on calcite dissolution kinetics in aqueous solutions at 25°C

The kinetics of calcite dissolution in solutions containing dissolved Ca²⁺ has been investigated at 25°C, using a rotating disc apparatus. In acid solutions no effect of Ca²⁺ in solution is observed. The rate is dependent on the transport of H⁺ to the surface. In neutral to alkaline solutions the dissolution reaction is controlled by mixed kinetics and the conventional empirical representation of the dissolution rate results through the interaction of chemical and transport gradients in the diffusion boundary layer. The chemical reaction rate is a function of the gradient between the equilibrium and the surface concentrations of calcium carbonate, whereas the transport reaction can be described in terms of a series of gradients between the surface and the bulk of dissolved calcium and carbonate species. The presence of dissolved Ca²⁺ decreases the rate of the transport reaction, making the dissolution process more transport-controlled. The chemical rate constant is independent of the Ca²⁺ concentration in solution. The chemical rate constant for Carrara marble dissolution is determined to ∼2·10⁻² cm s⁻¹ and the diffusion coefficient for the transport reaction to ∼7.6·10⁻⁶ cm² s⁻¹.In natural systems with high Ca²⁺ concentrations and in absence of inhibitors of the surface chemical reaction, the dissolution of calcite may approach a transport-controlled reaction, especially in environments with restricted flow.     

An experimental study of hydroxo complex formation in basic and near-neutral solutions of rare-earth elements and yttrium at 25 ºC

We have studied the hydrolytic behavior of Y^3 + and trivalent ions of rare earth elements in aqueous solutions at 25 ºC. The stepwise stability constants of hydroxide complexes were measured by spectrophotometry, using m-cresol purple and 1-(2-pyridylazo)-2-naphthol as pH indicators at an ionic strength no more than 0.0005. The results showed that at pH ranging between 6.0 and 11.0 in freshly prepared solutions of REE trichlorides, lanthanides are presented as Ln3 +, Ln(OH)2 +, Ln(OH)2, and Ln(OH)3. The plots of the formation constants of + 0 monohydroxo complexes of 4f n ions M^3 + versus atomic number Z deviate from smooth ones and consist of four convex curves. This phenomenon is also observed in normalized spectra of REE concentrations in natural objects and is known as the tetrad effect. The obtained data give an insight into the relationship between REE complex formation and REE fractionation in geochemical processes and can be used for physicochemical modeling of geochemical systems.     

Dependence of albite dissolution kinetics on ph and time at 25°c and 70°c

The dissolution rate of albite has been measured as a function of pH and time at 25°C and 70°C in a single-pass flow-through leaching apparatus. Run times extended to 50 days in each experiment. Limited data were obtained at 25°C in the pH range 4–10. More extensive data were obtained at 70°C over the pH range 1.39–11.75.Dissolution rates were defined by release of Si, and in some cases also by Al and Na releases. Speciationsolubility calculations indicate the solutions were well undersaturated for all the likely possible secondary minerals. The fluid was maintained far from equilibrium with albite in all runs. Analysis of the data shows a general consistency with the transition state theory model of Helgesonet al. (1984).Feldspars leached at low and high pH at 70°C showed extensive development of prismatic etch pits demonstrating a surface reaction-controlled dissolution process.     

Experimental study of Pd hydrolysis in aqueous solutions at 25–70°C

The hydrolysis of the Pd²⁺ ion in HClO₄ solutions was examined at 25–70°C, and the thermodynamic constants of equilibrium K ₍₁₎⁰ and K ₍₂₎⁰were determined for the reactions Pd²⁺ + H₂O = PdOH⁺ + H⁺ and Pd²⁺ + 2H₂O = Pd(OH)₂⁰ + 2H⁺, respectively. The values of log K ₍₁₎⁰ = −1.66 ± 0.5 (25°C) and −0.65 ± 0.25 (50°C) and log K ₍₂₎⁰ = −4.34 ± 0.3 (25°C) and −3.80 ± 0.3 (50°C) were derived using the solubility technique at 0.95 confidence level. The values of log K ₍₁₎⁰ = −1.9 ± 0.6 (25°C), −1.0 ± 0.4 (50°C), and −0.5 ± 0.3 (70°C) were obtained by spectrophotometric techniques. The palladium ion is significantly hydrolyzed at elevated temperatures (50–70°C) even in strongly acidic solutions (pH 1–1.5), and its hydrolysis is enhanced with increasing temperature.     

Dissolution kinetics of galena in acid NaCl solutions at 25—75 °C

Experiments on dissolution kinetics of galena were performed in 1 mol l⁻¹ NaCl solutions at pH 0.43–2.45 and 25–75 °C. When the dissolution reaction is far from equilibrium, a linear relation exits between the dissolution rate, r, and the H⁺ ion activity, [H⁺]. The rate law for galena dissolution is given by the following equation: r=k[H⁺]. With respect to H⁺, the dissolution reaction is in the first order. The apparent rate constant, k, has values of 2.34×10⁻⁷ mol m⁻² s⁻¹ at 25 °C, 1.38×10⁻⁶ mol m⁻² s⁻¹ at 50 °C, and 7.08×10⁻⁶ mol m⁻² s⁻¹ at 75 °C. The activation energy of dissolution reaction is 43.54 kJ mol⁻¹. The mechanism of dissolution is suggested to be surface chemical reaction, and the rate determining step is the dissociation of the Pb–S bond of the surface complex, which releases Pb²⁺ into the solution.     

Kaolinite and smectite dissolution rate in high molar KOH solutions at 35° and 80°C

Experiments measuring kaolinite and smectite dissolution rates were carried out using batch reactors at 35° and 80°C. No potential catalysts or inhibitors were present in solution. Each reactor was charged with 1 g of clay of the ≤2 μm fraction and 80, 160 or 240 ml of 0.1–4 M KOH solution. An untreated but sized kaolinite from St. Austell and two treated industrial smectites were used in the experiments. One smectite is a nearly pure montmorillonite, while the second has a significant component of beidellitic charge (35%). The change in solution composition and mineralogy was monitored as a function of time. Initially, the 3 clays dissolved congruently. No new formed phases were observed by XRD and SEM during the pure dissolution stage. The kaolinite dissolution is characterized by a linear release of silica and Al as a function of the log of time. This relationship can be explained by a reaction affinity effect which is controlled by the octahedral layer dissolution. Far from equilibrium, dissolution rates are proportional to a^0.56±0.12_OH⁻ at 35°C and to a^0.81±0.12_OH⁻ at 80°C. The activation energy of kaolinite dissolution increases from 33±8 kJ/mol in 0.1 M KOH solutions to 51±8 kJ/mol in 3 M KOH solutions. In contrast to kaolinite, the smectites dissolve at much lower rates and independently of the aqueous silica or Al concentrations. The proportionality of the smectite dissolution rate constant at 35 and 80°C was a^0.15±0.06_OH⁻. The activation energy of dissolution appears to be independent of pH for smectite and is found to be 52±4 kJ/mol. The differences in behavior between the two kinds of minerals can be explained by structural differences. The hydrolysis of the tetrahedral and the octahedral layer appears as parallel reactions for kaolinite dissolution and as serial reactions for smectite dissolution. The rate limiting step is the dissolution of the octahedral layer in the case of kaolinite, and the tetrahedral layer in the case of smectite.     

Experimental study of uraninite solubility in aqueous HCl solutions at 500°C and 1 kbar

Uraninite solubility in 0.001–2.0 m HCl solutions was experimentally studied at 500°C, 1000 bar, and hydrogen fugacity corresponding to the Ni/NiO buffer. It was shown that the following U(IV) species dominate in the aqueous solution: U(OH)₄⁰, U(OH)₂Cl₂⁰, and UOH Cl₃⁰ Using the results of uraninite solubility measurement, the Gibbs free energies of U(IV) species at 500°C and 1000 bar were calculated (kJ/mol): −9865.55 for UO₂(aq), −1374.57 for U(OH)₂ Cl₂⁰, and −1265.49 for UOH Cl₃⁰, and the equilibrium constants of uraninite dissolution in water and aqueous HCl solutions were estimated: UO₂(cr) = UO₂(aq), pK ₀ = 6.64; UO₂(cr) + 2HCl⁰ = U(OH)₂ Cl₂⁰, pK ₂ = 3.56; and UO₂(cr) + 3HCl⁰ = UOHcl₃⁰ + H₂O, pK ₃ = 3.05. The value pK ₁ ≈ 5.0 was obtained as a first approximation for the equilibrium UO₂(cr) + H₂O + HCl⁰ = U(OH)₃Cl⁰. The constant of the reaction UO₂(cr) + 4HCl⁰ = UCl₄⁰ + 2H₂O (pK ₄ = 7.02) was calculated taking into account the ionization constants of U Cl₄⁰ and U(OH)₄⁰, obtained by extrapolation from 25 to 500°C at 1000 bar using the BR model. Intense dissolution and redeposition of gold (material of experimental capsules) was observed in our experiments. The analysis and modeling of this phenomenon suggested that the UO_{2 + x} /UO₂ redox pair oxidized Au(cr) to Au⁺(aq), which was then reduced under the influence of stronger reducers.     

Synthesis of Pt- and Pd-sulphides in low temperature (85°C) solutions buffered by clay minerals and graphite: Preliminary results

Summary Some recent investigations of black shales reveal platinum-group element (PGE) concentrations in the ppm range. The low temperature nature of these mineralized sediments and their composition stimulated this first attempt to synthesize Pt- and Pd-phases in solutions at temperatures below 100°C under reducing conditions with H₂S flow through the solution. Experiments under controlled Eh-pH with montmorillonite presaturated in Pd and Pt in different chloride solutions resulted in the formation of Pt- and Pd-sulphides. PtS- and PdS-stability fields are very close to each other in Eh-pH values (400mV, 9). These data are in good agreement with those determined for some base metal sulphides synthesized at similar temperature by other researchers.The results may support the role of clay minerals as possible concentrators for PGE in the sedimentary environment.

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Synthese von Pt- und Pd-Sulfiden in gepufferten und mit Tonmineralen gesättigten Tieftemperaturlösungen (85°C)

Zusammenfassung Neuere Untersuchungen der Schwarzschiefer ergeben Konzentrationen an Platingruppenelementen (PGE) in ppm-Bereich. Niedrigtemperatur-Bedingungen und die Zusammensetzung der mineralisierten Sedimente gaben den Anlaß zur erstmaligen Synthese von Pt- und Pd-Phasen in H₂S-haltigen reduzierenden Lösungen bei Temperaturen unterhalb von 100°C. Bei Experimenten, die unter kontrollierten Eh-pH-Werten in unterschiedlichen Lösungen mit an Pd und Pt vorgesättigtem Montmorillonit durch-geführt wurden, konnte die Ausfällung von Pt- und Pd-Sulfiden nachgewiesen werden. Die Stabilitätsfelder der gebildeten PtS und PdS liegen nahe beieinander, bei Eh = 400 mV und pH = 9. Diese Bedingungen sind in Übereinstimmung mit den von anderen Autoren für einige Buntmetallsulfide bestimmten Daten unter ähnlichen Temperaturen.Die gewonnenen Ergebnisse bekräftigen die Rolle von Tonmineralen beim Absatz von PGE in sedimentärem Milieu.

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With 3 Figures     

An experimental study of phase equilibria in the system H2O-CO2-NaCl at 800 °C and 9 kbar

Phase equilibria in the ternary system H₂O-CO₂-NaCl were studied at 800 °C and 9 kbar in internally heated gas pressure vessels using a modified synthetic fluid inclusion technique. The low rate of quartz overgrowth along the `b' and `a' axes of quartz crystals was used to avoid fluid inclusion formation during heating, prior to attainment of equilibrium run conditions. The density of CO₂ in the synthetic fluid inclusions was calibrated using inclusions in the binary H₂O-CO₂ system synthesised by the same method and measured on the same heating-freezing stage. In the two-phase field, two types of fluid inclusions with different densities of CO₂ were observed. Using mass balance calculations, these inclusions are used to constrain the miscibility gap and the orientation of two-phase tie-lines in the H₂O-CO₂-NaCl system at 800 °C and 9 kbar. The equation of state of Duan et al. (1995) approximately describes the P-T section of the ternary system up to about 40 wt% of NaCl. At higher NaCl concentrations the measured solubility of CO₂ in the brine is much smaller than predicted by the EOS. A “salting out” effect must be added to the equation of state to include coulomb interaction in the model of Anderko and Pitzer (1993) and Pitzer and Jiang (1996). The new experimental data together with published data up to 5 kbar (Shmulovich et al. 1995) encompass practically all subsolidus crustal P-T conditions. A feature of the new experimental results is the large compositional range in the H₂O-CO₂-NaCl system occupied by the stability fields of halite + CO₂-rich fluid ± H₂O-NaCl brine. The prediction of halite stability in equilibrium with CO₂-rich fluid in deep-crustal rocks is supported by recent petrological and fluid inclusion studies of granulites. Received: 29 June 1998 / Accepted: 17 March 1999     

An experimental study of dissolution–reprecipitation in fluorapatite: fluid infiltration and the formation of monazite

In a series of timed experiments, monazite inclusions are induced to form in the Durango fluorapatite using 1 and 2 N HCl and H₂SO₄ solutions at temperatures of 300, 600, and 900°C and pressures of 500 and 1,000 MPa. The monazite inclusions form only in reacted areas, i.e. depleted in (Y+REE)+Si+Na+S+Cl. In the HCl experiments, the reaction front between the reacted and unreacted regions is sharp, whereas in the H₂SO₄ experiments it ranges from sharp to diffuse. In the 1 N HCl experiments, Ostwald ripening of the monazite inclusions took place both as a function of increased reaction time as well as increased temperature and pressure. Monazite growth was more sluggish in the H₂SO₄ experiments. Transmission electron microscopic (TEM) investigation of foils cut across the reaction boundary in a fluorapatite from the 1 N HCl experiment (600°C and 500 MPa) indicate that the reacted region along the reaction front is characterized by numerous, sub-parallel, 10–20 nm diameter nano-channels. TEM investigation of foils cut from a reacted region in a fluorapatite from the 1 N H₂SO₄ experiment at 900°C and 1,000 MPa indicates a pervasive nano-porosity, with the monazite inclusions being in direct contact with the surrounding fluorapatite. For either set of experiments, reacted areas in the fluorapatite are interpreted as replacement reactions, which proceed via a moving interface or reaction front associated with what is essentially a simultaneous dissolution–reprecipitation process. The formation of a micro- and nano-porosity in the metasomatised regions of the fluorapatite allows fluids to permeate the reacted areas. This permits rapid mass transfer in the form of fluid-aided diffusion of cations to and from the growing monazite inclusions. Nano-channels and nano-pores also serve as sites for nucleation and the subsequent growth of the monazite inclusions.     

The effect of malonate on the dissolution kinetics of albite,quartz, and microcline as a function of pH at 70°C

The effect of malonate on the dissolution rate of the reservoir minerals: albite, quartz, and microcline has been examined. The effect of pH on rate has been decoupled from the effect of the ligand by controlling pH using dilute buffer solutions at values of pH 4 through pH 10 at 70°C. Any effect of the buffer ligands (acetate and borate) or alkali cation (Na) on rate was accounted for by comparing the measured dissolution rates in buffer solutions with and without malonate. Flowing reactors were used and malonate concentration was varied from 1 to 100 mmolal.As malonate anion concentration is increased, the dissolution rate of these minerals also increases. At moderately acidic to near neutral pH in the solutions containing the highest malonate concentration, malonate most significantly increases the dissolution rate of the silicates over that expected due to simple hydrolysis. At alkaline pH the effect of malonate on the dissolution rate of these silicates is not significant, compared to the dissolution rate due to simple hydrolysis alone.     

Dissolution of quartz into dilute alkaline solutions at 90°C: A kinetic study

The rate of dissolution of Fontainebleau sand (pure quartz) into sodium hydroxide solutions (from 0.001 M to 0.5 M) has been determined at 90°C in well-stirred vessels. Dissolution leads to an equilibrium state, controlled by the solubility of quartz in pure water as undissociated silicic acid H₄SiO₄. As long as the initial molality of sodium hydroxide does not exceed 0.02 mol · kg⁻¹, the dissolution leads only to the formation of the three monomeric species H₄SiO₄, H₃SiO₄⁻ and H₂SiO₄²⁻, while polymers appear in the silica-rich solutions obtained in more alkaline media. The rate of dissolution can be represented by an adaptation of Stöber's model to alkaline solutions; the basic assumption is that the quartz surface is partially covered by a layer of adsorbed silicate ions, which represent an intermediate species between solid and dissolved silica.     

Does variscite control phosphate availability in acidic natural waters? An experimental study of variscite dissolution rates

The dissolution rates of natural, well crystallized variscite (AlPO₄·2H₂O) were determined from the evolution of aqueous Al and P concentrations in closed and open-system mixed-flow reactors at 25 °C and pH from 1.5 to 9.0. Measured dissolution rates decrease with increasing pH, from 6 × 10⁻¹⁶ mol/cm²/s at pH 1.5 to 5 × 10⁻¹⁷ mol/cm²/s at pH 5.89, and then increase with increasing pH to 4 × 10⁻¹⁶ mol/cm²/s at pH 9.0. Geochemical modeling calculations, performed using measured dissolution rates, indicate that it would take no more than a few weeks or months to equilibrate a mildly acidic, Al and P-free solution with variscite. Hence, variscite can buffer aqueous phosphate concentrations in mildly acidic near surface environments. This conclusion is confirmed by consideration of the compositions of natural waters.     

Calcite Dissolution in Deionized Water from 50°C to 250°C at 10 MPa: Rate Equation and Reaction Order

Carbonate minerals and water （or geofluids） reactions are important for modeling of geochemical processes and have received considerable attention over the past decades. The calcite dissolution rates from 50℃ to 250℃ at 10 MPa in deionized water with a flow rate varying from 0.2 to 5 mL/min were experimentally measured in a continuous flow column pressure vessel reactor. The dissolution began near the equilibrium with c/ceq 〉 0.3 and finally reached the equilibrium at 100℃-250℃, so the corresponding solubility was also determined as 1.87, 2.02, 2.02 and 1.88×10^-4.mol/L at 100℃, 150℃, 200℃ and 250℃ respectively, which was first increasing and then switching to decreasing with temperature and the maximum value might occur between 150℃ and 200℃. The experimental dissolution rate not only increased with temperature, but also had a rapid increase between 150℃ and 200℃ at a constant flow rate of 4 mL/min. The measured dissolution rates can be described using rate equations of R = k（1-c/ceq）n or R = kc-n. In these equations the reaction order n changed with temperature, which indicates that n was a variable rather than a constant, and the activation energy was 13.4 kJ/mol calculated with R = k（1-c/ceq）n or 18.0 kJ/mol with R = kc^-n, which is a little lower than the surface controlled values. The varied reaction order and lower activation energy indicates that calcite dissolution in this study is a complex interplay of diffusion controlled and surface controlled processes.     

Uranium(VI) in aqueous solutions at 25°C and a pressure of 1 bar: Insight from experiments and calculations

The behavior of the 0.1 mNaCl + 0.002 mHCl + 1.9 × 10^?5 mUO₂(NO₃)₂ solution was studied at pH from 2.7 to 11.0, 25°C, and 1 bar in an argon atmosphere. The curve of variations in U concentration exhibits two minima at pH = 6.6 ± 0.7 and 10.0 ± 0.5. These minima are related to the precipitation of schoepite and clarkeite, respectively. The experimental data were used to refine the stability constants of U(VI) (hydroxo) complexes. For the polymer species of U(VI) with charges from +2 to ?1, the method of additivity of thermochemical increments was used, and increments of the linear relation were determined for the calculation of the Gibbs free energies of formation (Δ_fG _298.15 ⁰ ) of respective homologue series. The proposed method was applied to calculate the Δ_fG _298.15 ⁰ of formation of U(VI) (hydroxo)complexes containing from one to five uranium atoms.