Generalized method for determining fluoroacidity by electrochemical diffusion coefficient measurement (application to HfF4)

A universal method for fluoroacidity evaluation was developed and based on a mass transport approach: it simply consists in measuring the diffusion coefficient of an electroactive species in various molten media. The reduction behaviour of Hf(IV) ions was investigated in molten fluorides and diffusion coefficients of Hf(IV) ions were measured. Results showed that diffusion coefficients decrease with fluoroacidity, due to the effect of solvent viscosity (which is linked to bridged fluorines). A global approach of mass transport in solution was then proposed, taking into account both solute and solvent. The Schmidt number (Sc) defined as the ratio between solvent viscosity and solute diffusivity was calculated in order to take into account these two parameters. Results showed that Sc increases with fluoroacidity, in a much more sensitive way than D. This universal method can extended to all electroactive species and to all bath fluoroacidity.