『Abstract
Previous experiments have indicated increased dissolution rates
of quartz in the presence of oxalate, although the mechanism responsible
is unclear. Possible explanations include a decrease in solution
saturation state due to the presence of an aqueous Si-oxalate
complex, or ligand promoted dissolution due to adsorption of oxalate
onto the quartz surface.
Formation of an aqueous Si-oxalate complex has been investigated
by titrating Si(OH)4 with K2C2O4. Formation of proposed
Si-oxalate complexes, such as a silicic acid-oxalate ester, should
result in pH shifts of the titration curve compared to blank titrations.
At an initial pH 5-6, titrations of Si(OH)4
solutions are identical to blank titrations (after correcting
for the buffering effect of silicic acid), indicating that Si-oxalate
complexing is negligible.
Oxalate adsorption onto quartz surfaces was studied for short-term
(4-5 h, pH 4.3-7.1, oxalate = 5-20μM) and long-term (1 week, autoclaved,
pH 6.3-7.0, oxalate = 10-40μM) experiments. Oxalate adsorption
under these conditions is negligible, with a maximum adsorption
of 3.0×10-9 mol/m2.
The lack of aqueous Si-oxalate complexing and oxalate adsorption
onto quartz indicate that these mechanisms will have no effect
upon the dissolution rate of quartz in oxalate solutions. Re-evaluation
of quartz dissolution rate data suggests that oxalate per se
has little or no effect upon quartz dissolution rates, and the
observed increase in dissolution rates with increasing oxalate
concentration may be due to the corresponding increase of Na+
concentration in solution.
Keywords: adsorption; complexing; dissolution rate; oxalate; quartz』
1. Introduction
2. Experimental methods
3. Results
3.1. Aqueous Si-oxalate complexing
3.2. Oxalate adsorption onto quartz
4. Discussion
5. Conclusions
Acknowledgements
References