Potentiometric studies of oxidation–reduction reactions with redox copolymers

Polymeric oxidants in the bead form that were macroporous styrene/divinylbenzene copolymers containing N‐chlorosulfonamide functional groups (in sodium or hydrogen form) or N‐bromosulfonamide groups (in sodium form) were synthesized and investigated to determine their oxidizing powers. The redox potentials of the N‐chlorosulfonamide/sulfonamide and N‐bromosulfonamide/sulfonamide systems were determined by potentiometric studies at different pH values with aqueous solutions of Na₂SO₃, KCN, and KSCN as reducers. The formal redox potentials of the N‐chlorosulfonamide copolymers were 0.79, 0.44, and ?0.12 V at pH's of 1.8, 8.45, and 13.6, respectively. The formal redox potential of the N‐bromosulfonamide copolymer was about 100 mV higher in comparable conditions and in solutions over pH = 5 (e.g., 0.56 V at pH = 8.56). The comparatively higher oxidizing power of the N‐bromosulfonamide copolymer was particularly evident in a strong alkaline medium (in which the N‐chlorosulfonamide copolymer was not reactive). In contrast, the N‐chlorosulfonamide copolymer showed strong oxidative properties in acidic media (in which the N‐bromosulfonamide copolymer decomposed itself). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008