The dissociation of carbonic acid in NaCl solutions as a function of concentration and temperature

Potentiometric measurements of the stoichiometric constants for the dissociation of carbonic acid in NaCl solutions ( and ) have been made as a function of molality (0-6 m) and temperature (0-50 °C). The results have been fitted to the equations

     

Stability constants for the formation of lead chloride complexes as a function of temperature and ionic strength

The stability constants for the formation of lead (Pb²⁺) with chloride

     

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:

     

Prediction of the vapor-liquid distribution constants for volatile nonelectrolytes in water up to its critical temperature

The distribution of solutes between coexisting liquid and vapor phases of water can be expressed by the distribution constant, K_D, defined as

     

The ionic strength dependence of lead (II) carbonate complexation in perchlorate media

Lead speciation in many aqueous geochemical systems is dominated by carbonate complexation. However, direct observations of Pb²⁺ complexation by carbonate ions are few in number. This work represents the first investigation of the equilibrium over a range of ionic strength. Through spectrophotometric observations of formation at 25 °C in NaHCO₃-NaClO₄ solutions, formation constants of the form were determined between 0.001 and 5.0 molal ionic strength. Formation constant results were well represented by the equation:

     

Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: Influence of solution complexation with carbonate

The influence of solution complexation on the sorption of yttrium and the rare earth elements (YREEs) by amorphous ferric hydroxide was investigated at 25 °C over a range of pH (4.0-7.1) and carbonate concentrations . Distribution coefficients, defined as , where [MS_i]_T is the total concentration of sorbed YREE, M_T is the total YREE concentration in solution, and [S_i] is the concentration of amorphous ferric hydroxide, initially increased in magnitude with increasing carbonate concentration, and then decreased. The initial increase of is due to sorption of YREE carbonate complexes , in addition to sorption of free YREE ions (M³⁺). The subsequent decrease of , which is more extensive for the heavy REEs, is due to the increasing intensity of YREE solution complexation by carbonate ions. The competition for YREEs between solution complexation and surface complexation was modeled via the equation:

     

A spectrophotometric study of Nd(III), Sm(III) and Er(III) complexation in sulfate-bearing solutions at elevated temperatures

The speciation of Nd(III), Sm(III), and Er(III) in sulfate-bearing solutions has been determined spectrophotometrically at temperatures from 25 to 250 °C and a pressure of 100 bars. The data obtained earlier on the speciation of Nd in sulfate-bearing solutions (Migdisov et al., 2006) have been re-evaluated and corrected using a more appropriate activity model and are compared with the corresponding data for Sm(III) and Er(III) and new data for Nd(III). Based on this comparison, the dominant species in the solution are interpreted to be and , with the latter complex increasing in importance at higher temperature. Equilibrium constants were calculated for the following reactions:

     

Arsenous acid ionisation in aqueous solutions from 25 to 300 °C

The ultraviolet spectra of dilute, aqueous arsenic (III)-containing solutions have been measured from 25 to 300 °C at the saturated vapour pressure. From these measurements, the equilibrium constant was obtained for the reaction

     

Oxygen isotope fractionation factors involving cassiterite (SnO2): II. determination by direct isotope exchange between cassiterite and calcite

Direct oxygen isotope fractionation between cassiterite and calcite has been investigated experimentally at 15 kbar with temperature ranging from 800 to 1000°C. Combined with the quartz-calcite fractionation measured with the same technique (Clayton et al., 1989), the calcite-cassiterite and quartz-cassiterite oxygen isotope fractionations can be expressed as:

     

Fluorite dissolution at acidic pH: In situ AFM and ex situ VSI experiments and Monte Carlo simulations

Dissolution of the fluorite (1 1 1) cleavage surface was investigated by means of in situ atomic force microscopy (AFM) and ex situ vertical scanning interferometry (VSI) experiments at pH range 1-3 in HCl solutions. Surface retreat was quantified at different pH values, yielding dissolution rates that were used to derive an empirical rate law for fluorite dissolution:

     

Solubility and speciation of sulfur in silicate melts: The Conjugated Toop-Samis-Flood-Grjotheim (CTSFG) model

A Conjugated Toop-Samis-Flood-Grjotheim (CTSFG) model is developed by combining the framework of the Toop-Samis polymeric approach with the Flood-Grjotheim theoretical treatment of silicate melts and slags. Electrically equivalent ion fractions are computed over the appropriate matrixes (anionic and cationic) in a Temkin notation for fused salts, and are used to weigh the contribution of the various disproportionation reactions of type:

     

Oxalate-promoted forsterite dissolution at low pH

We ran a series of 124 semi-batch reactor experiments to measure the dissolution rate of forsterite in solutions of nitric and oxalic acid solutions over a pH range of 0-7 and total oxalate concentrations between 0 and 0.35 m at 25 °C. We found that the empirical rate law for the dissolution of forsterite in these solutions is

     

The solubility of platinum and gold in NaCl brines at 1.5 kbar, 600 to 800°C: A laser ablation ICP-MS pilot study of synthetic fluid inclusions

The concentration and distribution of Pt and Au in a fluid-melt system has been investigated by reacting the metals with S-free, single-phase aqueous brines (20, 50, 70 wt% eq. NaCl) ± peraluminous melt at a confining pressure of 1.5 kbar and temperatures of 600 to 800 °C, trapping the fluid in synthetic fluid inclusions (quartz-hosted) and vesicles (silicate melt-hosted), and quantifying the metal content of the trapped fluid and glass by laser ablation ICP-MS. HCl concentration was buffered using the assemblage albite-andalusite-quartz and fO₂ was buffered using the assemblage Ni-NiO. Over the range of experimental conditions, measured concentrations of Pt and Au in the brines (, ) are on on the order of 1-10³ ppm. Concentrations of Pt and Au in the melt (, ) are ∼35-100 ppb and ∼400-1200 ppb, respectively. Nernst partition coefficients (, ) are on the order of 10²-10³ and vary as a function of (non-Henry’s Law behavior). Trapped fluids show a significant range of metal concentrations within populations of inclusions from single experiments (∼ 1 log unit variability for Au; ∼2-3 log unit variability for Pt). Variability in metal concentration within single inclusion groups is attributed to premature brine entrapment (prior to metal-fluid-melt equilibrium being reached); this allows us to make only minimum estimates of metal solubility using metal concentrations from primary inclusions. The data show two trends: (i) maximum and average values of and in inclusions decrease ∼2 orders of magnitude as fluid salinity () increases from ∼4 to 40 molal (20 to 70 wt % eq. NaCl) at a constant temperature; (ii) maximum and average values of increase approximately 1 order of magnitude for every 100°C increase temperature at a fixed . The observed behavior may be described by the general expression:

     

Sulfur diffusion in basaltic melts

We measured the diffusion coefficients of sulfur in two different basaltic melts at reduced conditions (i.e., in the sulfide stability field), temperatures from 1225°C to 1450°C, pressures of 0.5 and 1 GPa, and water concentrations of 0 and 3.5 wt%. Although each melt is characterized by slightly different sulfur diffusion coefficients, the results can be combined to create a general equation for sulfur diffusion in anhydrous basalts: