In this study MnO2 preparation by chemical methods is investigated for possible applications in dry cell batteries of chemical manganese dioxide (CMD) instead of electrolytic manganese dioxide (EMD). Three preparation procedures were tested: precipitation-oxidation by air plus acid activation (two-step-air), precipitation-oxidation by H2O2 plus acid activation (two-step-H2O2), precipitation-oxidation by KClO3 (singlestep-ClO3). Replicated factorial designs and related statistical analysis of experimental data by analysis of variance were performed in order both to obtain a preliminary optimization of the operating conditions and to take into account the intrinsic sample heterogeneity associated to each specific procedure. Comparisons among three different preparations denoted that in the investigated conditions two-step preparations give larger yields of activated solid in comparison with single-step preparation. Preliminary optimized conditions denoted final solid yields (80-86%) for both two-step procedures. The effect of operating conditions on the chemical, structural and electrochemical properties of CMDs produced in preliminary optimised conditions was investigated and compared with those of a commercial EMD sample by acid and acid-reducing leaching for Mn speciation in solid phase, potentiometric titrations, X-ray and IR spectra and cyclic voltammetry. These characterisation tests denoted the significant effect of acid activation in both preparation procedures to obtain CMD samples with high % of Mn(IV)oxides. Potentiometric titrations of solid samples obtained by first and second steps denoted that both procedures gives two CMD samples with the same acid-base properties, which in comparison with commercial EMD present a residual dissociation in the basic pH range (similar structure and proton insertion properties for CMDs and EMD, but different structural defects). X-ray and IR spectra of solid samples by first and second steps denoted highly disordered systems and the presence of Mn2O3 in first step products and of gamma-MnO2 in second step product. Voltammetric cycles denoted that CMD samples obtained after acid digestion present similar peaks than commercial EMD but with higher current intensity. (c) 2007 Elsevier B.V. All rights reserved.