Studies On Thermokinetics And Oxidation Of Phenols With Hydrogen Peroxide Catalyzed By Metallomicellar Mimetic Peroxidase

A novel thermokinetic research method, self-function regression method, has been proposed. The mathematical models of the thermokinetic research method for simple-order chemical reactions and for consecutive first order reaction have been established. The experimental results indicate that these thermokinetic research methods are believed to be correct. It is for the first time that the thermokinetic research method has been used to determine the kinetic parameters k1, k2 and k-1 of the reversible-consecutive first order reaction, and to research the kinetics of the oxidation of ascorbic acid with H2O2 in buffer solution and in CTAB micelle, respectively.The transient heat transport property in conduction calorimeter has been investigated and the thermal relaxation phenomena have been dissected and the distribution parameter model of the conduction calorimeter has been established. The thermal relaxation method proposed in this paper can be used to determine the faster reactions whose first-order rate constant could be less than 5 s-1 with conduction calorimeter.The copper dimethylglyoxime compound and the Cu(II) complex of a 14-membered tetra-aza-macrocyclic Schiff base ligand have been synthesized. The oxidations of hydroquinone with H202 catalyzed by these compounds have been investigated in aqueous solution and in CTAB micellar medium at 25 , respectively.The reaction kinetic constants have been calculated. The results indicate the metal lomicelle accelerate the oxidation of the reaction. The mathematical model, which can be used to treat quantitatively the kinetics of the catalytic oxidation reactions by metallomicelle, has been suggested.The metallomicelles are applied to the mimetic studies of peroxidase for the first time. The catalytic oxidation of phenol by hydrogen peroxide and using a synthetic copper( II) schiff base complex as catalyst has been investigated in 0.01M phosphate buffer(pH 7) at 25 . In order to further investigate the reaction pathway, the catalytic oxidation of hydroquinone, p-benzoquinone and catechol have been also carried out under the same conditions. And the reaction pathway for phenol oxidation catalyzed by the metal complex was proposed. The oxidation of phenol was also carried out in CTAB, SDS and Triton X-100 micellar media and the reactions kinetics were investigated, respectively. Addition of imidazole accelerates the oxidation of phenol. However the effect of pyridine on the reaction was very different from that of imidazole, the presence of pyridine affects greatly the distribution of products. The oxidative coupling reaction occurred in the presence of the metallomecellar mimetic peroxidase. And the mechanism of coupling reaction has been suggested. These studies are very important in theory and in application for treatment of wastewater containing phenols and for preparation of functional polymer.