In aqueous acid solution [Cr(CN)_6]^3- aquates via a series of stepwise stereospecific reactions to give [Cr(H_2O)_6]^3+ as the final product.Some of the intermediate cyanoaquo complexes in the sequence have been isolated.These complexes aquate by both acid independent and acid denpendent pathways,the latter involving protonation of the cyano ligands followed by aquation of the singly protonated species. The kinetic data for the aquation of [CrCN(H_2O)_5]^2+ are consistent with the transition state structure, [(H_2O)_4Cr(CN)-OH-Cr(H_2O)_5]^3+.Addition of Cr^2+ to solutions of cyanocobalt(III) complexes produces the metastable intermediate[CrNC(H_2O]^2)+.This isomerizes to in a Cr^2+ -catalyzed reaction which occurs by a ligand-bridged electron-change mechnism. From acid catalysis on these aquation reactions, it product HCN. Especially, HSO_3 ions do the role of catalyst in the formation of HCN from CrCN^3+.