PNNL

Abstract

Two disparate reaction mechanisms have been invoked to explain the reactivity of glass in contact with aqueous solution. One model is based on arguments from Transition State Theory (TST), which postulates that glass dissolution rates are surface reaction controlled. Alternatively, the second model argues that release of elements from glass to solution is governed by diffusion through an altered layer that forms on the surface of glass. Vertical Scanning Interferometry (VSI) is a new technique that allows one to observe surface features of specimens exposed to solution and may, potentially, be used to distinguish between competing models. We performed a series of dissolution experiments with a suite of glass compositions from chemically simple (sodium borosilicate) to complex (sixteen component borosilicate). Dissolution rates were determined using single-pass flow-through (SPFT) apparatus at 90ºC and pH = 9 and over a solution saturation interval. Upon termination of the experiments, glass coupons were examined by VSI techniques. Effluent chemistry and VSI measurements indicate a nearly constant rate of 2.2 to 3.4 g m-2 d-1 over the solution interval; rates calculated from both methods are identical within experimental uncertainty. We argue that this glass is phase separated, and propose a model for dissolution based on the relative rates of dissolution of the two glass compositions. The data are consistent with a modified version of TST and indicate the potency of VSI methods to elucidate glass reaction mechanisms.