共查询到20条相似文献，搜索用时 515 毫秒
1.
Dissolution rates of natural illite (Illite du Puy) were measured from Si release rates during closed system experiments at pH ranging from 1.4 to 12.4 and temperatures ranging from 5 to 50°C. Experiments performed at 4<pH<11 exhibited reactive fluid Si/Al concentration ratios that were inconsistent with stoichiometric illite dissolution likely due to secondary phase precipitation. In contrast, after an initial preferential release of aluminum relative to silicon, the reactive fluid Si/Al concentration ratio evolution was consistent with stoichiometric illite dissolution for all experiments conducted at 4>pH>11. Si release rate decreased with time during all experiments; for those experiments performed at 4>pH>11 this observation can be attributed to either 1) changing reactive surface area; 2) the effect of initial fine particle dissolution; or 3) a negative order of the illite dissolution reaction with respect to aqueous Al and/or Si. Measured dissolution rates exhibited a typical variation with pH; rates decrease with increasing pH at acid conditions, minimize at near to neutral pH and increase with increasing pH at basic conditions. An empirical expression describing rates obtained in the present study is given by
2.
The effect of pH on the kinetics of smectite (K-montmorillonite) dissolution was investigated at 50 and 70 °C in stirred flow-through reactors over the pH range of 1-13.5. Experiments done at very acidic and very basic pH were far from equilibrium. Near neutral pH experiments were closer to equilibrium. The Al/Si release ratio, while initially being incongruent, ultimately approached the stoichiometric value in most of the experiments. Temperature, extreme pH, and time favor congruency. Rates can be described by:
3.
Li Yang 《Geochimica et cosmochimica acta》2008,72(1):99-116
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
4.
Nicolas C.M. Marty Jordi Cama Daisuke Chino Angelina Razafitianamaharavo Jocelyne Brendlé Josep M. Soler Christophe Tournassat 《Geochimica et cosmochimica acta》2011,75(20):5849-5864
The effect of pH and Gibbs energy on the dissolution rate of a synthetic Na-montmorillonite was investigated by means of flow-through experiments at 25 and 80 °C at pH of 7 and 9. The dissolution reaction took place stoichiometrically at 80 °C, whereas at 25 °C preferential release of Mg over Si and Al was observed. The TEM-EDX analyses (transmission electronic microscopy with quantitative chemical analysis) of the dissolved synthetic phase at 25 °C showed the presence of newly formed Si-rich phases, which accounts for the Si deficit. At low temperature, depletion of Si concentration was attributed to incongruent clay dissolution with the formation of detached Si tetrahedral sheets (i.e., alteration product) whereas the Al behaviour remains uncertain (e.g., possible incorporation into Al-rich phases). Hence, steady-state rates were based on the release of Mg. Ex situ AFM measurements were used to investigate the variations in reactive surface area. Accordingly, steady-state rates were normalized to the initial edge surface area (11.2 m2 g−1) and used to propose the dissolution rate law for the dissolution reactions as a function of ΔGr at 25 °C and pH∼9:
5.
Far-from-equilibrium, steady-state dissolution rates at pH 4 of a suite of natural glasses, ranging from basaltic to rhyolitic in composition, have been determined as a function of aqueous fluoride concentrations up to 1.8 × 10−4 mol/kg in mixed-flow reactors. Dissolution rates of each of these glasses increase monotonically with increasing aqueous fluoride concentration. Measured dissolution rates are found to be consistent with both the Furrer and Stumm (1986) surface coordination model and the Oelkers (2001) multi-oxide dissolution model. Application of the latter model yields the following equation that can describe all measured rates as a function of both glass and aqueous solution composition:
6.
The steady state dissolution rate of San Carlos olivine [Mg1.82Fe0.18 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:
7.
Jordi Cama Li Zhang Giovanni De Giudici Andreas Lüttge 《Geochimica et cosmochimica acta》2010,74(15):4298-4311
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:
8.
9.
Claire Chaïrat Jacques Schott Jean-Eric Lartigue 《Geochimica et cosmochimica acta》2007,71(24):5901-5912
The dissolution rates of natural fluorapatite (FAP), Ca10(PO4)6F2, were measured at 25 °C in mixed-flow reactors as a function of pH from 3.0 to 11.7, and aqueous calcium, phosphorus, and fluoride concentration. After an initial preferential Ca and/or F release, stoichiometric Ca, P, and F release was observed. Measured FAP dissolution rates decrease with increasing pH at 3 ? pH ? 7, FAP dissolution rates are pH independent at 7 ? pH ? 10, and FAP dissolution rates again decrease with increasing pH at pH ? 10. Measured FAP dissolution rates are independent of aqueous Ca, P, and F concentration at pH ≈ 3 and pH ≈ 10.Apatite dissolution appears to be initiated by the relatively rapid removal from the near surface of F and the Ca located in the M1 sites, via proton for Ca exchange reactions. Dissolution rates are controlled by the destruction of this F and Ca depleted surface layer. The destruction of this layer is facilitated by the adsorption/penetration of protons into the surface at acidic conditions, and by surface hydration at neutral and basic conditions. Taking into account these two parallel mechanisms, measured fluorapatite forward dissolution rates can be accurately described using
10.
Keren Amram 《Geochimica et cosmochimica acta》2005,69(10):2535-2546
The main goal of this paper is to propose a new rate law describing the combined effect of pH (1 to 4.5) and temperature (25 to 70 °C) on smectite dissolution rate, under far from equilibrium conditions, as a step towards establishing the full rate law of smectite dissolution under acidic conditions. Dissolution experiments were carried out using non-stirred flow-through reactors fully immersed in a thermostatic water bath held at a constant temperature of 25.0°C, 50.0°C or 70.0°C ± 0.1°C. Smectite 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 smectite dissolution rate. Low Al/Si ratios were obtained in experiments that were conducted at pH ≥4. These low Al/Si ratios are explained by precipitation of gibbsite and/or diaspore.Dissolution rate increases with temperature and decreases with increasing pH. Dissolution rates of experiments in which ΔGr ≤ −21 kcal mol −1, are not affected by deviation from equilibrium. Dissolution rates in most experiments are not affected by the addition of up to 0.3 M NaNO3 to the input solution.A simple model is used to describe the combined effect of pH and temperature on smectite dissolution rate. According to this model, dissolution rate is linearly proportional to the concentration of adsorbed protons on the mineral surface, and proton adsorption is described using a Langmuir adsorption isotherm. All experimental results at pH <4 were fitted to the model using a multiple non-linear regression. The resulting rate law is:
(A1) 相似文献
11.
Richard T. Lowson Paul L. Brown Geetha Rajaratnam 《Geochimica et cosmochimica acta》2007,71(6):1431-1447
A model for the dissolution of chlorite has been developed based on fast ligand assisted proton attack of the alumina tetrahedra within the alumina-silica lattice followed by slower dissolution of the remnant silica lattice. While the rate determining step is within the silica dissolution regime, the rate is a function of the H+ and Al3+ concentrations and the dominant aqueous Al species. Individual rates may be described by a generic rate equation applicable across the spectrum of Al species:
12.
Eric H. Oelkers Jacques Schott Jean-Marie Gauthier Teresa Herrero-Roncal 《Geochimica et cosmochimica acta》2008,72(20):4948-4961
Steady-state muscovite dissolution rates have been measured at temperatures from 60 to 201 °C and 1 ? pH ? 10.3 as a function of reactive solution K, Si, and Al concentration. The pegmatitic muscovite used in these experiments has a composition consistent with (Na0.09, K0.86)Fe0.05Al2.92Si3.05O10(OH1.95, F0.06). All experiments were performed in titanium mixed-flow reactors. All experiments were performed at far-from-equilibrium conditions with respect to muscovite. All reactive solutions were undersaturated with respect to secondary product phases other than for some experiments which were supersaturated with respect to bohemite and diaspore; steady-state dissolution was stoichiometric for all experiments that were undersaturated with respect to these phases.The variation of rates with reactive solution composition depends on the solution pH. At pH ? 7 rates were found to decrease significantly with increasing reactive fluid Al activity but be independent of aqueous SiO2 activity. pH < 7 rates measured in the present study from 60 to 175 °C are consistent with
13.
The effects of organic acids on the dissolution of silicate minerals: A case study of oxalate catalysis of kaolinite dissolution 总被引：1，自引：0，他引：1
Jordi Cama 《Geochimica et cosmochimica acta》2006,70(9):2191-2209
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 < ΔGr < −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 (Cs,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:
14.
Amanda Albright Olsen 《Geochimica et cosmochimica acta》2008,72(7):1758-1766
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
15.
16.
The reaction between dissolved sulfide and synthetic iron (oxyhydr)oxide minerals was studied in artificial seawater and 0.1 M NaCl at pH 7.5 and 25°C. Electron transfer between surface-complexed sulfide and solid-phase Fe(III) results in the oxidation of dissolved sulfide to elemental sulfur, and the subsequent dissolution of the surface-reduced Fe. Sulfide oxidation and Fe(II) dissolution kinetics were evaluated for freshly precipitated hydrous ferric oxide (HFO), lepidocrocite, goethite, magnetite, hematite, and Al-substituted lepidocrocite. Reaction kinetics were expressed in terms of an empirical rate equation of the form:
17.
Steady-state talc dissolution rates, at far-from-equilibrium conditions, were measured as a function of aqueous silica and magnesium activity, pH from 1 to 10.6, and temperature from 25 to 150 °C. All rates were measured in mixed flow reactors and exhibited stoichiometric or close to stoichiometric dissolution. All measured rates at pH > 2 obtained at a fixed ionic strength of 0.02 M can be described to within experimental uncertainty using
18.
19.
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 KSP for the reaction
相似文献