Why need to add NaAlF6 to Al2O3?

The electrolysis of pure alumina faces some difficulties. Pure alumina is a bad conductor of electricity. The fusion temperature of pure alumina is about 2000 C and at this temperature when electrolysis is carried out on the fused mass, the metal formed vaporizes, as the boiling point of aluminium is 1800 ∘C. These difficulties are overcome by using a mixture containing alumina, cryolite (Na 3AlF 6), and fluorspar (CaF 2).

So in the electrolytic reduction of alumina, cryolite is added along with fluorspar to–
– decrease melting point of alumina
– decrease viscosity of electrolyte (CaF
2is used) – increase conductivity
Hope this helps