The effects of organic acids on the dissolution of silicate minerals: A case study of oxalate catalysis of kaolinite dissolution

Most studies agree that the dissolution rate of aluminosilicates in the presence of oxalic and other simple carboxylic acids is faster than the rate with non-organic acid under the same pH. However, the mechanisms by which organic ligands enhance the dissolution of minerals are in debate. The main goal of this paper was to study the mechanism that controls the dissolution rate of kaolinite in the presence of oxalate under far from equilibrium conditions (−29 < ΔG_r < −18 kcal mol⁻¹). Two types of experiments were performed: non-stirred flow-through dissolution experiments and batch type adsorption isotherms. All the experiments were conducted at pH 2.5-3.5 in a thermostatic water-bath held at a constant temperature of 25.0, 50.0 or 70.0 ± 0.1 °C. Kaolinite dissolution rates were obtained based on the release of silicon and aluminum at steady state. The results show good agreement between these two estimates of kaolinite dissolution rate. At constant temperature, there is a general trend of increase in the overall dissolution rate as a function of the total concentration of oxalate in solution. The overall kaolinite dissolution rates in the presence of oxalate was up to 30 times faster than the dissolution rate of kaolinite at the same temperature and pH without oxalate as was observed in our previous study. Therefore, these rate differences are related to differences in oxalate and aluminum concentrations. Within the experimental variability, the oxalate adsorption at 25, 50, and 70 °C showed the same dependence on the sum of the activities of oxalate and bioxalate in solution. The change of oxalate concentration on the kaolinite surface (C_s,ox) as a function of the sum of the activities of the oxalate and bioxalate in solution may be described by the general adsorption isotherm:

     

Heat capacity of ferrosilite, Fe2Si2O6

The heat capacity of synthetic ferrosilite, Fe₂Si₂O₆, was measured between 2 and 820 K. The physical properties measurement system (PPMS, Quantum Design^®) was used in the low-temperature region between 2 and 303 K. In the temperature region between 340 and 820 K measurements were performed using differential scanning calorimetry (DSC). The C _p data show two transitions, a sharp λ-type at 38.7 K and a small shoulder near 9 K. The λ-type transition can be related to collinear antiferromagnetic ordering of the Fe²⁺ spin moments and the shoulder at 10 K to a change from a collinear to a canted-spin structure or to a Schottky anomaly related to an electronic transition. The C _p data in the temperature region between 145 and 830 K are described by the polynomial $C_{p} {\left[ {\hbox{J\,mol}^{{ - 1}}\,{\hbox{K}}^{{ - 1}} } \right]} = 371.75 - 3219.2T^{{ - 1/2}} - 15.199 \times 10^{5} T^{{ - 2}} + 2.070 \times 10^{7} T^{{ - 3}} $ The heat content [H ₂₉₈ – H ₀] and the standard molar entropy [S ₂₉₈ – S ₀] are 28.6 ± 0.1 kJ mol^?1 and 186.5 ± 0.5 J mol^?1 K^?1, respectively. The vibrational part of the heat capacitiy was calculated using an elastic Debye temperature of 541 K. The results of the calculations are in good agreement with the maximum theoretical magnetic entropy of 26.8 J mol^?1 K^?1 as calculated from the relationship 2*Rln5.     

Testing fundamental physics with distant star clusters: theoretical models for pressure-supported stellar systems

We investigate the mean velocity dispersion and the velocity dispersion profile of stellar systems in modified Newtonian dynamics (MOND), using the N -body code n-mody , which is a particle-mesh-based code with a numerical MOND potential solver developed by Ciotti, Londrillo & Nipoti. We have calculated mean velocity dispersions for stellar systems following Plummer density distributions with masses in the range of 10⁴ to  10⁹ M_⊙  and which are either isolated or immersed in an external field. Our integrations reproduce previous analytic estimates for stellar velocities in systems in the deep MOND regime  ( a _i, a _e≪ a ₀)  , where the motion of stars is either dominated by internal accelerations  ( a _i≫ a _e)  or constant external accelerations  ( a _e≫ a _i)  . In addition, we derive for the first time analytic formulae for the line-of-sight velocity dispersion in the intermediate regime  ( a _i∼ a _e∼ a ₀)  . This allows for a much-improved comparison of MOND with observed velocity dispersions of stellar systems. We finally derive the velocity dispersion of the globular cluster Pal 14 as one of the outer Milky Way halo globular clusters that have recently been proposed as a differentiator between Newtonian and MONDian dynamics.     

The white dwarf luminosity function – II. The effect of the measurement errors and other biases

The disc white dwarf luminosity function is an important tool for studying the solar neighbourhood, since it allows the determination of several Galactic parameters, the most important one being the age of the Galactic disc. However, only the     method has been employed so far for observationally determining the white dwarf luminosity function, whereas for other kind of luminosity functions several other methods have been frequently used. Moreover, the procedures to determine the white dwarf luminosity function are not free of biases. These biases have two different origins: they can either be of statistical nature or a consequence of the measurement errors. In a previous paper we carried out an in-depth study of the first category of biases for several luminosity function estimators. In this paper we focus on the biases introduced by the measurement errors and on the effects of the degree of contamination of the input sample used to build the disc white dwarf luminosity function by different kinematical populations. To assess the extent of these biases we use a Monte Carlo simulator to generate a controlled synthetic population and analyse the behaviour of the disc white dwarf luminosity function for several assumptions about the magnitude of the measurement errors and for several degrees of contamination, comparing the performances of the most robust luminosity function estimators under such conditions.