Hydroxy Double Salt Anion Exchange Kinetics:  Effects of Precursor Structure and Anion Size^†

¹H NMR spectroscopy and powder X-ray diffraction have been used to explore the details of anion exchange reactions of two layered hydroxy double salts (HDSs), zinc copper hydroxy acetate (ZCA), nickel zinc hydroxy acetate (NZA), and a related layered material, zinc hydroxy acetate (ZHA), at room temperature (21−22 °C). Reactions that followed Avrami−Erofe'ev kinetics with respect to temporal profiles for acetate release, ZCA with butyrate (k = 1.7 × 10^-3 s^-1), and octanoate (k = 0.79 × 10^-3 s^-1) anions, as well as ZHA with octanoate (k = 2.6 × 10^-3 s^-1), demonstrate that rate constants for acetate release are influenced by the exchange anion relative size as well as by the solid precursor structure/composition. The reaction of NZA with octanoate deviated from expected Avrami−Erofe'ev behavior, with evidence for an intermediate species in the solid phase that may influence the rate of acetate release into solution. The reaction of ZCA with formate anions exhibited a unique zeroth-order kinetics release of acetate, providing the possibility of developing tunable nanostructured anion release sources by use of variations in the size of the exchange species.