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- W4241242412 abstract "By variation of the pH i.e. the acetate concentration, during oxidation of p-xylene in acetic acid/water mixtures and catalyzed by Co/Mn/Br, a maximum activity and selectivity is observed. The same is observed for the autoxidation of acetic acid by Co(II) acetate. If one operates at a lower or higher than the optimum pH, the rate of the formation of the desired product decreases and the rate of undesirable by-products increases. At sufficiently low pH the autoxidation reaction does not initiate. These observations can be rationalized by noting how the structures of the catalyst metal compounds change resulting in an increase in redox potentials of the metals as the acetate concentration decreases. Thus a thermodynamic balance of the required oxidation and reduction reactions of the metals is required. This explains why metal acetates i.e. basic compounds, are used as the initial catalytic species. Often autoxidation reactions are optimized by changing the catalyst concentration and it should be noted that this changes the pH as well. The pH dependence of the reactions that form undesirable by-products is summarized. The concept of thermodynamic and kinetic balance can also rationalize why metal/bromide catalysts are active while metal/fluoride, chloride, and iodide are either non-active or very weak." @default.
- W4241242412 created "2022-05-12" @default.
- W4241242412 date "2001-10-01" @default.
- W4241242412 modified "2023-10-18" @default.
- W4241242412 title "Author index to volume 31" @default.
- W4241242412 doi "https://doi.org/10.1016/s0167-9236(01)00118-x" @default.
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