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1916-2016

Sulphate as a selective redox buffer for borosilicate melts V34 66-70

Sulphate as a selective redox buffer for borosilicate melts V34 66-70

Two immiscible liquids form when excess sodium sulphate is mixed with a reference borosilicate melt under oxidising conditions at 1150C. The sulphate rich phase has no effect on the establishment of the individual Fe3+-Fe2+ , Mn3+ -Mn2 +, and Ce4+-Ce3+ redox equilibria in the coexisting borosilicate melt. Nor does it disturb the internal electron exchange reaction between iron and cerium within the borosilicate melt. However, the CrOi- -Cr3+ redox equilibrium in the borosilicate melt is controlled by the immiscible sulphate phase. Not only does the presence of the sulphate liquid effectively shift the equilibrium to form more CrOi- (chromate) at the expense of Cr3+ in the borosilicate melt, but it also preferentially incorporates jive times as much chromate. Even under relatively reducing conditions and/or in the presence of strong reducing agents such as Fe2+ and Mn2+ in the borosilicate melt, both of which should eliminate CrOi- from the system, significant concentrations of the chromate ion are incorporated into the sulphate phase. The SO:--SO2 redox couple 'buffers' the chromate content of the borosilicate melt by an internal electron exchange reaction driven by SO:- -00:- isomorphism.

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