Experimental study of the effect of pH on the kinetics of montmorillonite dissolution at 25 °C

The effect of pH on the kinetics of smectite (K-montmorillonite) dissolution was investigated at 25 °C in batch and stirred flow-through reactors over the pH range of 1-13.5, in KNO₃ solutions. Dissolution rates were obtained based on the release of Si and Al at steady-state under far from equilibrium conditions. Dissolution was non-stoichiometric between pH 5 and 10, due to adsorption/precipitation of Al. Dissolution rates computed from batch and flow-through experiments were consistent, irrespective of the Si and Al concentrations. Sample pre-treatment and the interlayer cation do not affect the steady-state dissolution rate or stoichiometry of cation release. The rate dependence on pH can be described by:

     

Kaolinite dissolution and precipitation kinetics at 22 °C and pH 4

Dissolution and precipitation rates of low defect Georgia kaolinite (KGa-1b) as a function of Gibbs free energy of reaction (or reaction affinity) were measured at 22 °C and pH 4 in continuously stirred flowthrough reactors. Steady state dissolution experiments showed slightly incongruent dissolution, with a Si/Al ratio of about 1.12 that is attributed to the re-adsorption of Al on to the kaolinite surface. No inhibition of the kaolinite dissolution rate was apparent when dissolved aluminum was varied from 0 and 60 μM. The relationship between dissolution rates and the reaction affinity can be described well by a Transition State Theory (TST) rate formulation with a Temkin coefficient of 2

     

Solubility of KFe(CrO4)2·2H2O at 4–75°C

The solubility of KFe(CrO₄)₂·2H₂O, a precipitate recently identified in a Cr(VI)-contaminated soil, was studied in dissolution and precipitation experiments. Ten dissolution experiments were conducted at 4–75°C and initial pH values between 0.8 and 1.2 using synthetic KFe(CrO₄)₂·2H₂O. Four precipitation experiments were conducted at 25°C with final pH values between 0.16 and 1.39. The log K_SP for the reaction

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Experimental determination of synthetic NdPO4 monazite end-member solubility in water from 21°C to 300°C: implications for rare earth element mobility in crustal fluids

The solubility of synthetic NdPO₄ monazite end-member has been determined experimentally from 21 to 300°C in aqueous solutions at pH = 2, and at 21°C and pH = 2 for GdPO₄. Measurements were performed in batch reactors, with regular solution sampling for pH measurement, rare earths and phosphorous analysis by inductively coupled plasma mass spectrometry (ICP-MS) coupled with a desolvation system. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed to check that no reprecipitation of secondary phases occurred and that the mineral surfaces remained those of a monazite. Coupled with speciation calculations, measured solution compositions permitted the determination of NdPO₄ and GdPO₄ solubility products which are in general agreement with previous experimental determination on rhabdophane at 25°C, but showing that monazite is more than two orders of magnitude less soluble than inferred on the basis of previous thermodynamic estimates. The temperature evolution from 21 to 300°C of the equilibrium constant (K) of the NdPO₄ monazite end-member dissolution reaction given by:

     

Sr/Ca and Ca/Ca fractionation during inorganic calcite formation: I. Sr incorporation

Partitioning of strontium during spontaneous calcite formation was experimentally studied using an advanced CO₂-diffusion technique. Results at different precipitation rates and T = 5, 25, and 40 °C show that at constant temperature Sr incorporation into calcite is controlled by the precipitation rate (R in μmol/m²/h) according to the individual expressions

     

A potentiometric study of the stability of aqueous yttrium-acetate complexes from 25 to 175 °C and 1-1000 bar

The stability of yttrium-acetate (Y-Ac) complexes in aqueous solution was determined potentiometrically at temperatures 25-175 °C (at P_s) and pressures 1-1000 bar (at 25 and 75 °C). Measurements were performed using glass H⁺-selective electrodes in potentiometric cells with a liquid junction. The species YAc²⁺ and were found to dominate yttrium aqueous speciation in experimental solutions at 25-100 °C (log [Ac⁻] < −1.5, pH < 5.2), whereas at 125, 150 and 175 °C introduction of into the Y-Ac speciation model was necessary. The overall stability constants β_n were determined for the reaction

     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

Interdiffusion of H2O and CO2 in metamorphic fluids at ∼490 to 690°C and 1 GPa

Interdiffusion coefficients have been determined for H₂O-CO₂ mixtures by quantifying the flux of CO₂ between two fluid-filled chambers in a specially designed piston-cylinder cell. The two chambers, which are maintained at 1.0 GPa and at temperatures differing by ∼100°C, each contain the X_CO2-buffering assemblage calcite + quartz + wollastonite, in H₂O. The positive dependence of X_CO2 on temperature results in a down-temperature, steady-state flux of CO₂ through a capillary tube that connects the two chambers. This flux drives the wollastonite = calcite + quartz equilibrium to the right in the cooler chamber, producing a measurable amount of calcite that is directly related to CO₂-H₂O interdiffusion rates. Diffusivities calculated from seven experiments range from 1.0 × 10⁻⁸ to 6.1 × 10⁻⁸ m²/s for mean capillary temperatures between ∼490 and 690°C. The data set can be approximated by an Arrhenius-type relation:

     

Molybdic acid ionisation under hydrothermal conditions to 300 °C

This UV spectrophotometric study was aimed at providing precise, experimentally derived thermodynamic data for the ionisation of molybdic acid (H₂MoO₄) from 30 to 300 °C and at equilibrium saturated vapour pressures. The determination of the equilibrium constants and associated thermodynamic parameters were facilitated by spectrophotometric measurements using a specially designed high temperature optical Ti-Pd flow-through cell with silica glass windows.The following van’t Hoff isochore equations describe the temperature dependence of the first and second ionisation constants of molybdic acid up to 300 °C:

     

Dissolution kinetics of fosteritic olivine at 90-150 °C including effects of the presence of CO2

The steady state dissolution rate of San Carlos olivine [Mg_1.82Fe_0.18 SiO₄] in dilute aqueous solutions was measured at 90, 120, and 150 °C and pH ranging from 2 to 12.5. Dissolution experiments were performed in a stirred flow-through reactor, under either a nitrogen or carbon dioxide atmosphere at pressures between 15 and 180 bar. Low pH values were achieved either by adding HCl to the solution or by pressurising the reactor with CO₂, whereas high pH values were achieved by adding LiOH. Dissolution was stoichiometric for almost all experiments except for a brief start-up period. At all three temperatures, the dissolution rate decreases with increasing pH at acidic to neutral conditions with a slope of close to 0.5; by regressing all data for 2 ? pH ? 8.5 and 90 °C ? T ? 150 °C together, the following correlation for the dissolution rate in CO₂-free solutions is obtained:

     

Surface properties, solubility and dissolution kinetics of bamboo phytoliths

Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of “soil” phytoliths ( at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH_IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for “soil” (native) and “heated” (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-pK surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ? pH ? 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation:

     

Precipitation and mixing properties of the “disordered” (Mn,Ca)CO3 solid solution

The enthalpy of mixing of the calcite-rhodochrosite (Ca,Mn)CO₃ solid solution was determined at 25 °C from calorimetric measurements of the enthalpy of precipitation of solids with different compositions. A detailed study of the broadening of powder X-ray diffraction peaks shows that most of the precipitates are compositionally homogeneous. All the experimental enthalpy of mixing (ΔH^m) values are positive and fit reasonably well (R² = 0.86) to a Guggenheim function of three terms:

     

A simple predictive model of quartz solubility in water-salt-CO2 systems at temperatures up to 1000 °C and pressures up to 1000 MPa

Knowledge of the solubility of quartz over a broad spectrum of aqueous fluid compositions and T-P conditions is essential to our understanding of water-rock interaction in the Earth’s crust. We propose an equation to compute the molality of aqueous silica, m_SiO2(aq), mol·(kg H₂O)⁻¹, in equilibrium with quartz and water-salt-CO₂ fluids, as follows:

     

Precipitation of poorly crystalline antigorite under hydrothermal conditions

Magnesium silicate precipitation experiments were carried out in alkaline solutions in the temperature range 39°C-150°C. Titrations were carried out at room temperature where the pH of an aqueous solution containing magnesium and silica was raised to bring about precipitation of a magnesium silicate. The precipitation of the magnesium silicate was rapid. Equilibrium between the solution and the precipitate was attained in a period of less than one hour up to a month at around 90°C, depending on the initial degree of oversaturation. Relative magnesium and silica depletion in the experimental solutions and IR spectra of the precipitate show that the magnesium silicate resembles poorly developed antigorite (p-antigorite). Values for its solubility constant were obtained and an equation describing its solubility in the temperature interval 0°-200°C calculated. The equation is: log K_sp = 9303/T + 3.283, where T is in K, and it is valid for the following reaction:

     

An experimental study of magnesite dissolution rates at neutral to alkaline conditions and 150 and 200 °C as a function of pH, total dissolved carbonate concentration, and chemical affinity

Steady-state magnesite dissolution rates were measured in mixed-flow reactors at 150 and 200 °C and 4.6 < pH < 8.4, as a function of ionic strength (0.001 M ? I ? 1 M), total dissolved carbonate concentration (10⁻⁴ M < ΣCO₂ < 0.1 M), and distance from equilibrium. Rates were found to increase with increasing ionic strength, but decrease with increasing temperature from 150 to 200 °C, pH, and aqueous CO₃²⁻ activity. Measured rates were interpreted using the surface complexation model developed by Pokrovsky et al. (1999a) in conjunction with transition state theory (Eyring, 1935). Within this formalism, magnesite dissolution rates are found to be consistent with

     

The kinetics of the dissolution of chlorite as a function of pH and at 25°C

Far from equilibrium, quasi-steady state dissolution rates of an iron rich chlorite (Mg_2.76Fe²⁺_1.90Fe³⁺_0.07Al_0.97)[Si_2.48Al_1.52O₁₀](OH)₈, have been measured as a function of H⁺ concentration for the pH range 3 to 10.5 and at 25°C. The rates were determined using a single pass flow through cell and with a time frame for observing the steady state condition of between 10 to 50 days. Rates are independent of the buffers used to control the pH, sample preparation, experimental methodology and chlorite composition. The results were collated with literature values allowing the rate to be expressed as a function of H⁺ as;

     

Kinetics of gypsum crystal growth from high ionic strength solutions: A case study of Dead Sea - seawater mixtures

Gypsum precipitation kinetics were examined from a wide range of chemical compositions , ionic strengths (4.75-10 m) and saturation state with respect to gypsum (1.16-1.74) in seeded batch experiments of mixtures of Ca²⁺-rich Dead Sea brine and -rich seawater. Despite the variability in the experimental solutions, a single general rate law was formulated to describe the heterogeneous precipitation rate of gypsum from these mixtures: