Authors: PuchkovS.V., NepomnyashchikhYu.V., PecherinaK.D.

Title of the article: Determination of kinetic parameters of the liquid-phase oxidation of organic compounds by oxygen at initiation by azobisisobutyronitrile and tert-butylhydroperoxide

Year: 2018, Issue: 3, Pages: 70-78

Branch of knowledge: Chemical technology

Index UDK: 544.421.081.7

DOI: 10.26730/1999-4125-2018-3-70-78

Abstract: The article offers the way of processing the experimental results received at liquid-phase oxidation of organic compounds by oxygen in the Howard-Ingold conditions. The method can be used to determine kinetic parameters of such reactions. Within the offered approach, the scheme of the experiment and mathematical methods of calculation are developed. The optimum values of parameters of the kinetic equations were de-termined using a program based on the least-squares method. The objective function was optimized by the Fletcher-Reeves conjugate gradient method. Determination of kinetic parameters was carried out on the exam-ple of liquid-phase oxidation of 2-butanol by oxygen in the presence of azobisisobutyronitrile and tert-butyl hydroperoxide. Oxidation rate was measured on manometric setup. The initiation efficiency with azobisisobutyronitrile was estimated on consumption of inhibitor – ionol. Concentration of inhibitor was determined by gas-liquid chromatography. From the dependencies of rate of oxygen uptake on initiation rates at the expense of azobisisobutyronitrile decomposition at liquid-phase oxidation of 2-butanol in chlorobenzene in the presence of tert-butyl hydroperoxide, initial approximations of kinetic parameters of liquid-phase oxidation of alcohol in the conditions of the mixed initiation are calculated. Using the received initial approximations of kinetic parameters in the optimization of all experimental data array, the following values have been defined: oxidability parameter, the ratio of the peroxyl radicals recombination rate constants with and without chain termination, rates of initiation with tert-butyl hydroperoxide.

Key words: liquid-phase oxidation kinetic parameters the Howard-Ingold method mixed initiation conjugate gradient method 2-butanol

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