Ion Exchange, Thermal Transformations, and Oxidizing Properties of Birnessite

Abstract Synthetic sodium bimessite, having a cation-exchange capacity (CEC) of 240 meq/100 g (cmol/kg) was transformed into Li, K, Mg, Ca, Sr, Ni, and Mn 2+ cationic forms by ion exchange in an aqueous medium. Competitive adsorption studies of Ni and Ba vs. Mg showed a strong preference for Ni and Ba by bimessite. The product of Mg 2+ -exchange was buserite, which showed a basal spacing of 9.6 Å (22°C, relative humidity (RH) = 54%), which on drying at 105°C under vacuum collapsed to 7 Å. Of the cation- saturated bimessites with 7-Å basal spacing, only Li-, Na-, Mg-, and Ca-bimessites showed cation exchange. Heating bimessite saturated with cations other than K produced a disordered phase between 200° and 400°C, which transformed to well-crystallized phases at 600°C. K-exchanged bimessite did not transform to a disordered phase; rather a topotactic transformation to cryptomelane was observed. Generally the larger cations, K, Ba, and Sr, gave rise to hollandite-type structures. Mn- and Ni-bimessite transformed to bixbyite-type products, and Mg-bimessite (buserite) transformed to a hausmannite-type product. Li-bimessite transformed to cryptomelane and at higher temperature converted to hausmannite. The hollandite-type products retained the morphology of the parent bimessite. The mineralogy of final products were controlled by the saturating cation. Products obtained by heating natural bimessite were similar to those obtained by heating bimessite saturated with transition elements.