Multivariate Statistical Analysis of Chemical and Electrochemical Oscillators for an Accurate Frequency Selection

The effect of experimental parameters on the frequency of chemical oscillators has been systematically studied since the first observations of clock reactions. The approach is mainly based on univariate changes in one specific parameter while others are kept constant. The frequency is then monitored and the effect of each parameter is discussed separately. This type of analysis, however, does not take into account the multiple interactions among the controllable parameters and the synergic responses on the oscillation frequency. We have carried out a multivariate statistical analysis of chemical (BZ-ferroin catalyzed reaction) and electrochemical (Cu/Cu2O cathodic deposition) oscillators and identified the contributions of the experimental parameters on frequency variations. The BZ reaction presented a strong dependence on the initial concentration of sodium bromate and temperature, resulting in a frequency increase. The concentration of malonic acid, the organic substrate, affects the system but with lower intensity compared with the combination of sodium bromate and temperature. On the other hand, the Cu/Cu2O electrochemical oscillator was shown to be less sensitive to changes in the temperature. The applied current density and pH were the two parameters which most perturbed the system. Interestingly, the frequency behaved nonmonotonically with a quadratic dependence. The multivariate analysis of both oscillators exhibited significant differences - while the homogenous oscillator displayed a linear dependence with the factors, the heterogeneous one revealed a more complex dependence with quadratic terms. Our results may contribute, for instance, in the synthesis of self-organized materials in which an accurate frequency selection is required and, depending on its value, different physicochemical properties are obtained.