Crystal surface reactivity analysis using a combined approach of X-ray micro-computed tomography and vertical scanning interferometry

Abstract

Dissolution rates of porous crystalline materials reflect the superposition of transport and surface control, mainly via the parameters saturation of the ambient fluid and distribution of surface energy. As a result, reacting surfaces evolve over time showing a heterogeneous distribution of surface rates. The spatiotemporal heterogeneity of surface reaction rates is analyzed using the rate map and rate spectra concept. Here, we quantify the dissolution rate variability covering the nm- to mm-scale of dissolving single-crystal and polycrystalline calcite samples, using a combined approach of X-ray micro-computed tomography (μ-CT) and vertical scanning interferometry (VSI). The dissolution experiments cover reaction periods from 15 minutes up to 54 days. The observed rate ranges are remarkably consistent over the entire reaction period but include a variability of about two orders of magnitude (10⁻⁹ − 3 × 10⁻⁷ mol m⁻² s⁻¹). The rate map data underscore the concurrent and superimposing impact of surface- vs. fluid flow controlled rate portions. The impact of fluid flow on reactivity at the mm-scale in the transport-controlled system is confirmed by 2-D reactive transport modeling. The sub-mm spatial heterogeneity of low vs. high reactivity surface portions of polycrystalline calcite is clearly below the mean crystal size. This suggests the dominant impact of highly reactive surface portions irrespective of the orientation of larger crystals on the overall surface reactivity. Correspondingly, the overall range of intrinsic reactivity heterogeneity as observed using singly crystal material is not further expanded for polycrystalline material. As a general conclusion, numerical reactive transport concepts would benefit from the implementation of a reactivity term resembling the experimentally observed existence of multiple rate components.