The importance of chemical mechanisms in sonochemical modelling.

A state-of-the-art chemical mechanism is introduced to properly describe chemical processes inside a harmonically excited spherical bubble placed in water and saturated with oxygen. The model uses up-to-date Arrhenius-constants, collision efficiency factors and takes into account the pressure-dependency of the reactions. Duplicated reactions are also applied, and the backward reactions rates are calculated via suitable thermodynamic equilibrium conditions. Our proposed reaction mechanism is compared to three other chemical models that are widely applied in sonochemistry and lack most of the aforementioned modelling issues. In the governing equations, only the reaction mechanisms are compared, all other parts of the models are identical. The chemical yields obtained by the different modelling techniques are taken at the maximum expansion of the bubble. A brief parameter study is made with different pressure amplitudes and driving frequencies at two equilibrium bubble sizes. The results show that due to the deficiencies of the former reaction mechanisms employed in the sonochemical literature, several orders of magnitude differences of the chemical yields can be observed. In addition, the trends along a control parameter can also have dissimilar characteristics that might lead to false optimal operating conditions. Consequently, an up-to-date and accurate chemical model is crucial to make qualitatively and quantitatively correct conclusions in sonochemistry.

Relationship between the radial dynamics and the chemical production of a harmonically driven spherical bubble.

The sonochemical activity and the radial dynamics of a harmonically excited spherical bubble are investigated numerically. A detailed model is employed capable to calculate the chemical production inside the bubble placed in water that is saturated with oxygen. Parameter studies are performed with the control parameters of the pressure amplitude, the forcing frequency and the bubble size. Three different definitions of collapse strengths (extracted from the radius vs.time curves) are examined and compared with the chemical output of various species. A mathematical formula is established to estimate the chemical output as a function of the collapse strength; thus, the chemical activity can be predicted without taking into account the chemical kinetics into the bubble model. The calculations are carried out by an in-house code exploiting the high processing power of professional graphics cards (GPUs). The results shown that chemical activity can be approximated qualitatively from the values of relative expansion. This could be helpful in order to optimise chemical output of sonochemical reactors either from measurement data or simulations as well.