The effect of pH on kaolinite dissolution rates and on activation energy

1995 ◽  
Vol 59 (6) ◽  
pp. 1037-1052 ◽  
Author(s):  
Jiwchar Ganor ◽  
Jose Luis Mogollón ◽  
Antonio C. Lasaga
Keyword(s):  
Activation Energy ◽  
Dissolution Rates ◽  
Effect Of Ph

Hydrothermal Transformation of Inorganic and Biogenic Silica as Studied Using in Situ Hydrothermal Infrared Microspectroscopy

2018 ◽  
Vol 72 (10) ◽  
pp. 1487-1497
Author(s):  
Naoto Morifuji ◽  
Satoru Nakashima
Keyword(s):  
Activation Energy ◽  
Rate Constants ◽  
Biogenic Silica ◽  
Zero Order ◽  
Silica Gels ◽  
Dissolution Rates ◽  
First Order ◽  
Order Rate ◽  
Hydrothermal Transformation

Infrared (IR) spectral changes with time of biogenic and inorganic silica have been examined using in situ IR micro-spectroscopy by using an original hydrothermal diamond cell. Centric diatoms (diameters = 100–350 µm) and silica gels (C-300, Wako Chemicals) were heated at 125–185 ℃ range with a pressure of 3 MPa. Decreases of 950 cm−1 (Si–OH) peak heights could be fitted by a combination of exponential and linear decreases (y = A1 exp (−k1t) − k0 t + A0). The first-order rate constants k1 [s−1] for Si–OH decreases of diatoms and silica gels are similar but the activation energy was lower for diatoms (61 kJċmol−1 < 106 kJċmol−1). The first-order rate constants k1 [s−1] for Si–OH decreases of diatoms and silica gels are much faster than reported hydrothermal transformation rates of silica (Opal A to Opal CT and Opal CT to quartz). These results indicate that the exponential Si–OH decreases observed in biogenic and inorganic silica during hydrothermal reactions are considered to correspond to dehydration–condensation reactions in the amorphous states (Si–OH + HO–Si → Si–O–Si). In fact, band area ratios 1220 cm−1/1120 cm−1 increased exponentially indicating more bridging of Si–O–Si. On the other hand, the linear decreases of Si–OH of silica gels (k0 [s−1]) were considered to be due to dissolution of silica. By using the grain size and density of silica gels, the zero-order dissolution rate constants k0* [molċm−2ċs−1] were calculated from k0 [s−1]. The obtained dissolution rates k0* are larger than reported values for silica glass and quartz. The zero-order dissolution rates k0 [s−1] for diatoms are similar to those for silica gels but with a lower activation energy (32 kJċmol−1 < 60 kJċmol−1). The smaller activation energy values for diatoms than silica gels both for the first and zero-order decrease rates of Si–OH might indicate catalytic effects of organic components bound to biogenic silica for the dehydration–condensation reaction and dissolution. The present in situ hydrothermal IR micro-spectroscopy is useful for characterizing transformation of amorphous materials including inorganic–organic composites.

scholarly journals Estimating the activation energy of bond hydrolysis by time-resolved weighing of dissolving crystals

2021 ◽  
Vol 5 (1) ◽  
Author(s):  
Philippe Ackerer ◽  
Arnaud Bouissonnié ◽  
Raphael di Chiara Roupert ◽  
Damien Daval
Keyword(s):  
Activation Energy ◽  
Crystal Surface ◽  
Calibration Method ◽  
Solute Concentration ◽  
Bond Breaking ◽  
Dissolution Rates ◽  
Experimental Conditions ◽  
Time Resolved ◽  
Crystal Dissolution ◽  
Dissolution Model

AbstractBond-breaking activation energy EB is nowadays a key parameter for understanding and modeling crystal dissolution processes. However, a methodology to estimate EB based on classical dissolution experiments still does not exist. We developed a new method based on the calibration of a Kossel type dissolution model on measured dissolution rates obtained by mass (or volume) variations over time. The dissolution model does not depend on the geometry of the crystal surface but only on the density of the different types of sites (kink, step, terrace, bulk). The calibration method was applied to different experimental setups (flow through and batch) with different ways of estimating the dissolution rates (solute concentration in the fluid, surface topography) for calcite crystals. Despite the variety of experimental conditions, the estimated bond-breaking activation energies were very close to each other (between 31 and 35 kJ/mol) and in good agreement with ab initio calculations.

Chemical Durability of Aluminosilicate Glasses Containing Low Solubility Chemical Elements

1997 ◽  
Vol 506 ◽  
Author(s):  
G. Leturcq ◽  
G. Berger ◽  
T. Advocat ◽  
C. Fillet ◽  
C. Halgand ◽  
...  
Keyword(s):  
Activation Energy ◽  
Chemical Elements ◽  
Glass Network ◽  
Chemical Durability ◽  
Complexing Agent ◽  
Chemical Compositions ◽  
Protective Film ◽  
Dissolution Rates ◽  
Network Modifier ◽  
Aluminosilicate Glasses

ABSTRACTThe chemical durability of aluminosilicate glasses was investigated experimentally between 90 and 200°C. In order to evaluate their potential for containment of minor actinides, these glasses were doped with Nd (to simulate the presence of trivalent actinides) or U. The proportions of the glass network formers, Si and Al, were near those found in basaltic glasses (tholeitic end members). The differences between the chemical compositions allow the clarification of the influence of glass network modifier elements on the chemical durability of silica glasses. More precisely, we tested the ability of Ti, Zr, Nd and N to potentially improve the chemical durability.Two types of leach tests were conducted:Dynamic leach tests to determine the initial dissolution rates at 90, 150 and 200°C and the activation energy (Ea) of the glass dissolution reaction;Static leach tests at high SA/V (200 cm−1) and 90°C to determine the long-term alteration rates and the apparent silica solubility.For all the glass compositions tested, the initial dissolution rates at nearly neutral or weakly basic pH are similar at the same temperature. Consequently all aluminosilicate glasses have the same activation energy, 60 kJ/mol. This suggests that the initial hydrolysis mechanism is controlled by the breakdown of Si-O and/or Al—O bonds, whatever the nature of glass network modifier elements.On the other hand, modifier elements have major effects on the formation of protective films at the glass surface. The nature of this protective film depends on the chemical composition of the glass. A phenomenon similar to metal passivation, has been observed on a glass highly enriched with Nd (53.8 oxide wt%) which may lead to alteration rates in undersaturated media up to two orders of magnitude lower than those observed for basaltic glasses. This “passivation” effect disappears when a sodium sulfate solution (a Nd complexing agent) is used as a leachant. Nitrogen does not improve the chemical durability of aluminosilicate glasses. Finally, all these glasses have the same low dissolution rate (10−4 g/m2/day) under saturated conditions.

Aqueous dissolution kinetics of pyrochlore, zirconolite and brannerite at 25, 50, and 75 °C

2000 ◽  
Vol 88 (9-11) ◽  
Author(s):  
S. K. Roberts ◽  
W.L. Bourcier ◽  
H.F. Shaw
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Dissolution Rate ◽  
Dissolution Kinetics ◽  
Kcal Mole ◽  
Dissolution Rates ◽  
Flow Through ◽  
Kinetics Of ◽  
Total Dissolution ◽  
Calculated Average

We measured the rates of dissolution of pyrochlore, zirconolite, and brannerite in pH-buffered solutions of pH 2, 4, 6, 8, 10, and 12 at temperatures of 25, 50, and 75 °C in flow-through reactors. The dissolution rates for all phases show a minimum near pH 8. Zirconolite dissolves the slowest of the three phases, with a slightly higher rate for pyrochlore and a much higher dissolution rate for brannerite. Brannerite dissolves as much has 30 times faster than zirconolite. The rates increase with temperature, but the magnitude of the increase varies with pH. The calculated average apparent activation energy for dissolution is 6±3 kcal/mole. Dissolution is non-stoichiometric at all pHs. Ti and Hf are released most slowly, and are often below detection limits (1 ppb for Ti, 0.2 ppb for Hf). Releases of Ca, U, Gd, and Ce appear to be stoichiometric below pH 8. At pH 8 and above only U is measurable in solution. Dissolution rates are slow under all conditions, and commonly in the range of 1-100 nm total dissolution/year (between 10

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