Do tetrachloroaluminate salts hydrolyse?
NaAlCl4 will hydrolyze according to the following reaction $$\ce{AlCl4^- + \ 2H2O -&gt;  Al(OH)2^+  +  2 H+ +4 Cl-}$$and if there is enough water it could goo further away like $$\ce{AlCl4^- + \ 3H2O -&gt;  Al(OH)3  +  3 H+ +4 Cl-}$$ But the reaction will never produce $\ce{NaAl(OH)4}$ as you think. The substance $\ce{NaAl(OH)4}$ can only be produced in very basic solution, and here the solution is acidic.