III International Conference

PP-II-135THE LOW-TEMPERATURE CATALYTIC OXIDATION OF VARIOUSSUBSTRATES BY OXYGEN IN THE PRESENCE OF NITROGEN OXIDES ANDTHE COMPLEXES OF TRANSITION METALSTaltenov A.A., Sarmurzina A.G., Emelyanova V.S.Scientific research institute of New chemical technologies and materials of Kazakh NationalUniversity, Almaty, KazakhstanE-mail: rinctm@kazsu.kzNitric acid very frequently is used in the industry of organic synthesis at oxidation oforganic compounds. Disadvantage of nitric acid is the evolution of sample quantity ofnitrogen oxides. The similar effect is observed at oxidizing metals manufacturing fromsulphidic ores. Practical interest is represented with recycling in such processes nitrogen(III-V) oxides not as oxidizers, but as catalysts of substrates oxidation by oxygen. It is shown, thatat the presence of transition metal complexes and nitrogen(II, IV) oxides it is carried out lowtemperatureoxidation of a lot of substrates by oxygen. The reactions kinetic is investigated bymodern methods (IR-, UF- spectrophotometry, GL-chromatography, redox-potentiometry,volumetry), quantum-chemical characteristics of the intermediate particles participating inreactions calculated by NDO method. The scheme of the mechanism is offered.Study of the processes kinetics specified in table 1, has shown, that oxidation rate ofvarious substrates by oxygen is described by the kinetic equation (1):WO2k2⋅ CNO⋅ CO⋅ k2 1 ⋅ CS⋅ CNO2= , (1)k ⋅ C + k ⋅ C ⋅ C1Swhere S – a substratum reacting with oxygen, k1 and k2 – rate constants of reactions (2, 3):2NOO2k1NO + S←⎯→NO SO(2)2+k2NO+ O2 ← 2⎯→2NO2(3)Table 1 – Low-temperature (40-60 °С) oxidation of various substratum by oxygen atpresence nitrogen oxides and complexes of transition metalsProcess Catalysts k 1 , mole/l⋅s k 1 , l 2 /mole 2 ⋅sC 6 H 5 OH + O 2 → C 6 H 4 O 2 NO, NO 2 , CuCl 2 7⋅10 -2 9,3⋅10 62H 2 S + O 2 → 2H 2 O + 2S2 (C 6 H 5 )S + O 2 → 2C 2 H 5 OH + 2SC 6 H 4 Cl 2 + O 2←⎯⎯O →H 2 C 6 H 5 O 2 + 2HClNO, NO 2 , I- 8,3⋅10 -1 8,7⋅10 6NO, NO 2 , CuCl 2 1,3⋅10 -1 8,8⋅10 6NO, NO 2 , I- 5⋅10 -2 8,6⋅10 6C 6 H 6 + HBr + O 2 → C 6 H 4 Br 2 + H 2O NO, NO 2 , Co(NO 3 ) 2 8,6⋅10 -3 8,7⋅10 6411