Kinetics And Mechanism Of Oxidation Of Some Carboxylic Acids, Alcohol Ethers And Acids Amides Organic Compound By Ni （Ⅳ）Complex

The studies of oxidation of some organic compounds by dihydroxydiperiodatonickelate complex, previous workers who applied inprotonated complex()()223 62 Ni OH H IO-? ?? ? as existed form. Our group thinks that the existed form should be()()42 62 2Ni OH H IO-? ?? ?, by lonization form the activation center, forming the intermediate adduct with the reductant and obtain the product through electron transfer.The kinetics of oxidations of 5-sulphosalicylic acid, Sulfanilic, 2-(2-methoxyetthoxy)-ethanol, 2-(2-ethoxyethoxy)-ethanol, N, N-dimethylformamide and N, N-dimethylacetamid by dihydroxydiperiodatonickelate were studied by spectrophotometry in this paper. Through the experiments, we obtained the medium conditions, studied the influence of [reductant], [OH-], [IO4-] and ionic strength for the reaction rates. Found the optimal reaction conditions. According to the macroscopical orderliness of the reaction and the activation center that was supposed, the related mechanism was deduced.Through the study we found that the reactions were first order to 5-sulphosalicylic acid, 2-(2-methoxyetthoxy)-ethanol, 2-(2-ethoxyethoxy)-ethanol, N, N-dimethylformamide and N, N-dimethylacetamid, but was fraction order to the Sulfanilic. By the study of alcohol ethers and acids amides organic we found that the length of the cabon chain and the strength of the electronic that influence the reaction rates. 2-(2-ethoxyethoxy)-ethanol>2-(2-methoxyetthoxy)- ethanol, N, N-dimethylacetamid> N, N-dimethylformamide.The supposed mechanism can explain the experimental phenomena. We obtained the determining-step rate constants at different temperatures and calculated the activation parameters at 298.2K. Through the experiments and discussion, proving that the existence of low-pronotonated form was more reasonable. Through the study and experiments of the dihydroxydiperiodatonickelate oxidation of the organic compounds, not only provides new valuable information for the study of the kinetics, but also gives the important guiding significance for the development of the dihydroxydiperiodatonickelate.