『Abstract
The effect of pH on the kinetics of smectite (K-montmorillonite)
dissolution was investigated at 50 and 70℃ 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:
R (mol g-1 s-1) = 10-9.00aH+0.58 + 10-9.70aOH-0.38 + 10-12.15 at
50℃
R (mol g-1 s-1) = 10-8.25aH+0.75 + 10-8.70aOH-0.42 + 10-11.95 at
70℃
Dissolution rates decrease with increasing pH under acid conditions,
minimize at near neutral pH and increase with increasing pH under
basic conditions. Apparent activation energies are pH-dependent
and have a maximum of 19.3 kcal mol-1 at pH 1, a minimum
of 5.3 kcal mol-1 between pH 4-7 and another maximum
of 20.3 kcal mol-1 at pH 11. Protons, water, and hydroxyls
promote dissolution. Their relative contribution to the overall
dissolution rate depends on pH.』
1. Introduction
1.1. Previous studies on smectite dissolution rate
2. Materials and methods
2.1. Characterization of the montmorillonite
2.2. Experimental design
2.3. Kinetics calculations
3. Results and discussion
3.1. Flow-through experiments at 50℃ and 70℃
3.2. Stoichiometry
3.3. Saturation state of the solutions
3.4. Dissolution Rate Laws
3.5. Comparison to previous studies
3.6. Rate constants, reaction orders and reaction mechanism
4. Conclusions
Acknowledgments
References