Let be the measured mass concentration of element , its blank concentration, the leachate volume, the element's mass fraction in the original glass, and the exposed glass surface area. For one closed test, the normalised elemental release isIf concentration is in , volume in litres and area in square metres, is in of glass-equivalent release. Dividing by removes the trivial difference caused by loading different amounts of the measured element; dividing by removes the first-order geometrical scale difference. Normalising only by initial element content or reporting raw solution concentration does not accomplish both corrections.
For repeated sampling with leachant replacement, use cumulative released mass: add the mass removed in all earlier aliquots to the mass present in the final remaining solution, with the corresponding blank correction. A flow-through experiment instead integrates over time. State how surface area was determined and whether it is held at its initial value in the reported normalisation; cracks, fines and alteration can change the genuinely reactive area.
Compare for several constituents. In congruent glass dissolution, the different element-normalised curves coincide, provided the released elements remain in solution. Preferential early alkali release can indicate ion exchange, whereas lower dissolved silicon or actinide release can reflect an alteration layer, sorption or secondary-phase precipitation. boron is often useful as a relatively mobile dissolution tracer, but not if the leachant contains a large boron background or if it is itself retained. A low aqueous concentration of one constituent is therefore not automatically a low glass-dissolution rate.
A near-linear interval gives an approximately constant normalised elemental release rate. A square-root time dependence can be consistent with diffusion-limited transport, and decreasing slopes can indicate saturation or a protective alteration layer; no one curve shape proves a unique mechanism. Compare solution inventories with the altered solid by microscopy, composition and phase analysis. Differences in pH, temperature, leachant composition, duration and surface-area-to-volume ratio remain even after this mass-and-area normalisation. Careful background subtraction and control of solution conditions are experimentally consequential, as demonstrated in primary flow-through measurements.[ref]
Measurement of kinetic rate law parameters on a Na-Ca-Al borosilicate glass for low-activity waste by B. P. McGrail and others. Journal of Nuclear Materials 249, 175–189; abstract on duration, background subtraction and solution-condition dependence
Use a single-pass flow-through leach test. A controlled leachant passes once over a known glass surface area, and successive effluent samples are analysed after the initial transient. temperature and pH are controlled, and fresh solution removes dissolved products so that they do not accumulate towards saturation with respect to the dissolving glass. This approaches the forward glass dissolution rate at those specified conditions.
At steady state, with expressed as volume per time,Increase across a series of tests until the normalised rate becomes independent of further dilution, within analytical uncertainty. A genuine plateau supports approach to the dilute-solution limit; it should not be assumed from one arbitrarily chosen flow rate. Check blanks, inlet concentrations, temperature, pH, actual flow, fines and exposed surface area. At high flow the concentration increment becomes small, so an uncorrected background can manufacture an apparent rate increase.
The resulting maximum is the forward rate for the specified temperature, pH and glass, not an absolute maximum over every possible environment. It also differs from the lower residual rate that can develop in a static, product-rich leachate. Primary measurements demonstrate the method and the importance of background subtraction and flow variation.[ref]
Measurement of kinetic rate law parameters on a Na-Ca-Al borosilicate glass for low-activity waste by B. P. McGrail and others. 1997, experimental method and abstract, including the nonphysical flow-rate increase caused by inadequate background subtraction